TWI585134B - Dispersion composition and method of manufacturing the same, curable composition using the same, transparent film, micro lens, and solid-state image sensing device - Google Patents

Description

Dispersion composition, method for producing the same, curable composition using the same, transparent film, microlens, and solid-state imaging element

The present invention relates to a dispersion composition, a curable composition using the same, a transparent film, a microlens, and a solid-state imaging element.

As a microlens used in an imaging optical system of an on-chip color filter such as an electronic photocopier or a solid-state imaging device, or an optical wiring used instead of a copper wiring, it is desirable to form a refractive index high and fine. A composition for forming a transparent member such as a transparent film or a transparent wiring.

In particular, as the solid-state imaging element is continuously miniaturized, the microlens used in the solid-state imaging element is required to be finer, and high refractive index is required to achieve higher-efficiency condensing. For example, a composition for forming a microlens having a high refractive index coated with titanium oxide particles or a composition for forming a solid-state imaging element is disclosed (for example, see Patent Document 1 and Patent Document 2). In particular, in recent years, with the high picture quality, the size of one pixel is extremely small, and it is required to collect light more efficiently. Therefore, a microlens having a higher refractive index is required. In addition, in order to make more components by one manufacturing, The size of the wafer to be used also becomes large, and in this case, the coating surface shape tends to be deteriorated.

On the other hand, Patent Document 3 discloses a dispersion resin having a specific structure capable of improving the dispersibility of an organic pigment for use in a color filter. Further, Patent Document 4 discloses a composition for forming a high refractive index material containing a dispersion resin of the above specific structure and inorganic fine particles.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-179678

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-185683

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-277514

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-239923

However, the composition for forming a high refractive index material as described above has a problem that the unevenness of the coating surface is caused by unevenness on the surface of the film after the composition is applied onto the substrate or the like. .

As a result of intensive studies, the inventors of the present invention found that the deterioration of the coating surface is caused by the fact that the dispersion resin has a high acid value (for example, an acid value of 120 mgKOH/g or more) and the above-mentioned dispersion resin. The acid groups are agglomerated with each other to cause phase separation between the inorganic fine particles and the above-mentioned dispersion resin.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a dispersion composition having a high refractive index and a surface shape of a film surface after application, and a curable composition, a transparent film, a microlens, and a solid using the same. Photography component.

Specific means for solving the above problems are as follows.

<1>

a dispersion composition comprising: a metal oxide particle (A) having a primary particle diameter of 1 nm to 100 nm; a polymer compound (B) represented by the following formula (1) having an acid value of less than 120 mgKOH/g; And solvent (C).

In the above formula (1), R ¹ represents a (m+n)-valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ represents at least one selected from the group consisting of an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, an alkyl group, an aryl group, and a stretching group. Alkoxy chain group, oxime imine group, alkoxycarbonyl group, alkylaminocarbonyl group, carboxylate group, sulfonylamino group, heterocyclic group, alkoxyalkyl group, epoxy group, isocyanate group and A monovalent substituent of a group in the group consisting of hydroxyl groups. The n A ¹ and R ² may be the same or different.

m is a positive number of 8 or less, n is 1 to 9, and m+n is 3 to 10.

P ¹ represents a polymer chain. m P ^{1 's} may be the same or different.

<2>

The dispersion composition according to <1>, wherein the polymer compound (B) has a weight average molecular weight of 5,000 to 8,000.

<3>

The dispersion composition according to <1> or <2>, wherein the polymer compound (B) has an acid value of 70 mgKOH/g to 90 mgKOH/g.

<4>

The dispersion composition according to any one of the above aspects, wherein the content of the metal oxide particles (A) with respect to the total solid content of the dispersion composition is 65 mass% or more.

<5>

The dispersion composition according to any one of the above aspects, wherein the polymer compound (B) is a polymer compound represented by the following formula (2).

In the above formula (2), R ³ represents a (m+n)-valent linking group, and R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group. A ² represents at least one selected from the group consisting of an acid group, a urea group, an urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, an alkyl group, an aryl group, and a stretching group. Alkoxy chain group, oxime imine group, alkoxycarbonyl group, alkylaminocarbonyl group, carboxylate group, sulfonylamino group, heterocyclic group, alkoxyalkyl group, epoxy group, isocyanate group and A monovalent substituent of a group in the group consisting of hydroxyl groups. The n A ² and R ⁴ may be the same or different. m is a positive number of 8 or less, n represents 1 to 9, and m+n satisfies 3 to 10.

P ² represents a polymer chain. m P ² and R ⁵ may be the same or different.

<6>

<1> to <5> The dispersion composition according to any preceding claim, wherein A ¹ in the general formula or the general formula (2) (1) A ² is in containing at least one acidic group selected from the group consisting of a phenol group, an alkyl group, an aryl group, a group having an alkylene oxide chain, a hydroxyl group, a urea group, a urethane group, a sulfonylamino group, a quinone imine group, and a group having a coordinating oxygen atom A monovalent substituent of a group in the group consisting of.

<7>

The dispersion composition according to any one of <1> to <5>, wherein A ¹ in the above formula (1) or A ² in the above formula (2) contains at least one pKa of 5 or more A monovalent substituent of a functional group.

<8>

The dispersion composition according to <7>, wherein the functional group having a pKa of 5 or more is a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, a urea group, or a urethane group. An alkyl group, an aryl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, a group having an alkylene oxide chain, a quinone imine group, a carboxylate group, a sulfonylamino group, a hydroxyl group or a heterocyclic group.

<9>

The dispersion composition according to any one of <1> to <8> wherein the polymer chain represented by P ¹ or P ² is derived from a polymer or copolymer selected from a vinyl monomer, and an ester system. Polymerization of at least one of a polymer, an ether polymer, a urethane polymer, a guanamine polymer, an epoxy polymer, an fluorenone polymer, and a modified or copolymer thereof Chain of things.

<10>

The dispersion composition according to any one of <1> to <9> wherein the polymer chain represented by P ¹ or P ² contains at least one repeating unit, and the number of repeats k of the at least one repeating unit is 3~60.

<11>

The dispersion composition according to any one of <1> to <10>, wherein R ¹ in the above formula (1) or R ³ in the above formula (2) is any one of the following formulae The base represented.

In the above formula, L ₃ represents a trivalent group. T ₃ represents a single bond or a divalent linking group, and three T ₃ groups may be the same or different.

L ₄ represents a tetravalent group. T ₄ represents a single bond or a divalent linking group, and four T ₄ groups may be the same or different.

L ₅ represents a pentavalent group. T ₅ represents a single bond or a divalent linking group, and five of T ₅ may be the same or different.

L ₆ represents a hexavalent group. T ₆ represents a single bond or a divalent linking group, and six T ₆ groups may be the same or different.

<12>

The dispersion composition according to any one of the above aspects, wherein the polymer compound (B) is a polymer compound represented by the following formula (5).

In the above formula (5), R ⁶ represents a (m+n1+n2)-valent linking group, and R ⁷ to R ⁹ each independently represent a single bond or a divalent linking group.

A ³ represents a monovalent substituent containing at least one acid group. A ⁴ represents a monovalent substituent different from A ³ . The n1 A ³ and R ⁷ may be the same or different. N2 A ⁴ and R ⁸ may be the same or different. m is a positive number of 8 or less, n1 represents 1 to 8, n2 represents 1 to 8, and m+n1+n2 satisfies 3 to 10.

P ³ represents a polymer chain. m P ³ and R ⁹ may be the same or different.

<13>

A sturdy composition, which comprises the dispersion composition according to any one of <1> to <12>, and the polymerizable compound (D).

<14>

The curable composition according to <13>, wherein the polymerizable compound (D) is a compound selected from the group consisting of two or more epoxy groups or oxetanyl groups in the molecule, and two or more terminal ethylene groups. At least one of the group consisting of compounds having a sexual unsaturated bond.

<15>

The curable composition according to <13> or <14>, which further comprises at least one selected from the group consisting of a polymerization initiator (E) and a binder polymer.

<16>

The curable composition according to <15>, wherein the polymerization initiator (E) is an oxime polymerization initiator.

<17>

The curable composition according to any one of <13> to <16> which is used for forming a microlens or an undercoat film for forming a color filter.

<18>

A transparent film which is formed using the curable composition according to any one of <13> to <17>.

<19>

A microlens formed using a transparent film obtained by the curable composition as described in <17>.

<20>

A solid-state imaging element comprising the microlens of <19>.

<21>

A method for producing a dispersion composition, which comprises the dispersion composition according to any one of <1> to <12>.

Further, the present invention preferably has the following constitution.

<22>

A method of producing a transparent film, comprising: a step of applying a curable composition according to any one of <13> to <17> on a wafer; a first heating step immediately following; This is followed by a second heating step at a temperature higher than the temperature of the first heating step described above.

<23>

A method for producing a microlens, comprising the step of post-baking a transparent film as described in <18>, and further comprising a dry etching step.

<24>

A method for producing a solid-state imaging device, comprising: a step of forming a red pixel, a blue pixel, and a green pixel on a substrate for a solid-state imaging device having at least a photodiode, a light shielding film, and a device protective film; a step of heating and curing the curable composition according to any one of <13> to <17>; forming a resist pattern; performing a post-baking treatment to form the formed resist pattern Lenticular shape Steps; Dry etching step.

According to the present invention, it is possible to provide a dispersion composition having a high refractive index and a surface shape of a film surface after coating, a curable composition using the same, a transparent film, a microlens, and a solid-state imaging element.

1‧‧‧TFT (thin film transistor)

2‧‧‧Wiring

3,8‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7, 18‧‧‧ contact holes

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

16‧‧‧TFT

17‧‧‧ hardened film

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

30‧‧‧Electrostatic type input device

31‧‧‧ front panel

32‧‧‧mask layer

33‧‧‧First transparent electrode pattern

33a‧‧‧Pie section

33b‧‧‧Connected section

34‧‧‧Second transparent electrode pattern

35‧‧‧Insulation

36‧‧‧Electrical elements

37‧‧‧Transparent protective layer

38‧‧‧ openings

FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10.

2 is a conceptual diagram showing an example of an organic electroluminescence (EL) display device.

3 is a cross-sectional view showing the configuration of a capacitance type input device.

4 is a schematic view showing a configuration of a capacitance type input device.

FIG. 5 is an explanatory view showing an example of a first transparent electrode pattern and a second transparent electrode pattern in the present invention.

In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The description of the constituent elements described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene. Mercapto and methacrylonitrile. In addition, in this specification, "single quantity" and "monomer" have the same meaning. The monomer in the present invention is different from the oligomer and the polymer, and means a compound having a mass average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a single amount or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

In addition, in this specification, unless otherwise indicated, "refractive index" means the refractive index with respect to the light of the wavelength of 635 nm.

<dispersed composition>

The dispersion composition of the present invention includes a metal oxide particle (A) having a primary particle diameter of 1 nm to 100 nm, a polymer compound (B) represented by the following formula (1) having an acid value of less than 120 mgKOH/g, And solvent (C).

In the above formula (1), R ¹ represents a (m+n)-valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ represents at least one selected from the group consisting of an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, an alkyl group, an aryl group, and a stretching group. Alkoxy chain group, oxime imido group, heterocyclic group, alkoxycarbonyl group, alkylaminocarbonyl group, carboxylate group, sulfonylamino group, alkoxyalkyl group, epoxy group, isocyanate group and A monovalent substituent of a group in the group consisting of hydroxyl groups. The n A ¹ and R ² may be the same or different.

m is a positive number of 8 or less, n is 1 to 9, and m+n is 3 to 10.

P ¹ represents a polymer chain. m P ^{1 's} may be the same or different.

In the dispersion composition of the present invention, the substituent A ^{1 of the} polymer compound (B) can interact with the metal oxide particles (A), so that the polymer compound (B) has n (1) The substituents A ¹ can stably interact with the metal oxide particles (A). In addition, the m polymer chains P ^{1 of the} polymer compound (B) function as a steric repulsion group, and by having m, it is possible to exhibit a good steric repulsion force and to uniformly disperse the metal oxide particles. Further, it is presumed that the polymer compound (B) does not cause aggregation or the like of the particles in the molecular structure, and the aggregation of the particles is caused by cross-linking between particles by a conventional grafting random dispersion agent. Condensed.

<(A) Metal oxide particles having a primary particle diameter of 1 nm to 100 nm>

The metal oxide particles (A) in the present invention are preferably inorganic particles having a high refractive index and being colorless, white or transparent, and examples thereof include titanium (Ti), zirconium (Zr), aluminum (Al), and antimony (Si). Oxide particles of zinc (Zn) or magnesium (Mg), preferably titanium dioxide (TiO ₂ ) particles, zirconium dioxide (ZrO ₂ ) particles or cerium oxide (SiO ₂ ) particles, more preferably titanium dioxide Particles (hereinafter, sometimes referred to as "titanium dioxide").

The titanium dioxide particles in the present invention may be represented by the chemical formula TiO ₂ , and preferably have a purity of 70% or more, more preferably 80% or more, and still more preferably 85% or more. The low-valent titanium oxide, titanium oxynitride, etc. represented by the general formula Ti _n O _2n-1 (n represents the number of 2 to 4) is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

The metal oxide particles in the present invention are not particularly limited as long as the primary particle diameter is from 1 nm to 100 nm, and can be suitably selected from commercially available metal oxide particles, for example.

The primary particle diameter of the metal oxide particles is from 1 nm to 100 nm, preferably from 1 nm to 80 nm, particularly preferably from 1 nm to 50 nm. When the primary particle diameter of the metal oxide particles exceeds 100 nm, the refractive index and the transmittance may decrease. Further, when the primary particle diameter of the metal oxide particles is less than 1 nm, the dispersibility may be lowered due to aggregation.

Further, in the present invention, the average particle diameter can also be used as an index of the primary particle diameter. The average particle diameter of the metal oxide particles in the present invention means a value obtained by diluting a mixed liquid or dispersion containing metal oxide particles to 80 times by using propylene glycol monomethyl ether acetate, and using dynamic light scattering. The value obtained by measuring the obtained diluent.

The average particle size of the metal oxide particles is set to use Nikkiso Co., Ltd. The manufactured Microtrac UPA-EX150 was subjected to the number average particle diameter obtained by the measurement.

In the present invention, the refractive index of the metal oxide particles is not particularly limited, but from the viewpoint of obtaining a high refractive index, it is preferably from 1.75 to 2.70, more preferably from 1.90 to 2.70.

Further, the specific surface area of the metal oxide particles is preferably from 10 m ² /g to 400 m ² /g, more preferably from 20 m ² /g to 200 m ² /g, most preferably from 30 m ² /g to 150 m ² /g.

Further, the shape of the metal oxide particles is not particularly limited. For example, it may be in the form of rice grains, spheres, cubes, spindles or indefinite shapes.

The metal oxide particles in the present invention may also be surface-treated by an organic compound. Examples of the organic compound used for the surface treatment include a polyol, an alkanolamine, a stearic acid, a decane coupling agent, and a titanate coupling agent. Among them, a decane coupling agent is preferred.

The surface treatment can be carried out by using a single surface treatment agent, or by combining two or more kinds of surface treatment agents.

Further, it is also preferred that the surface of the metal oxide particles is covered with an oxide such as aluminum, tantalum or zirconia. Thereby, the weather resistance is further improved.

As the metal oxide particles in the present invention, commercially available ones can be preferably used.

As a commercial item of the titanium dioxide particle, the TTO series (TTO-51 (A), TTO-51 (C), etc.), TTO-S, V series (TTO-S-1) manufactured by Ishihara Industry Co., Ltd. are mentioned, for example. , TTO-S-2, TTO-V-3, etc.), MT series (MT-01, MT-05, etc.) manufactured by Tayca (shares).

As a commercial item of the zirconia particles, for example, UEP (manufactured by the first rare element chemical industry (share)), PCS (manufactured by Nippon Electric Co., Ltd.), JS-01, JS-03, JS-04 (for example) Nippon Electric (manufactured by the company), UEP-100 (first diluted chemical industry (share) manufacturing).

As a commercially available product of the cerium oxide particles, for example, OG502-31 manufactured by Clariant Co., and the like can be mentioned.

In the present invention, the metal oxide particles may be used singly or in combination of two or more.

The content of the metal oxide particles in the dispersion composition of the present invention (or a curable composition to be described later) is preferably 65% by mass based on the total solid content of the dispersion composition from the viewpoint of obtaining a high refractive index. More preferably, it is 70 mass% or more.

The upper limit of the content is not particularly limited, but is preferably 90% by mass or less, and more preferably 85% by mass or less based on the total solid content of the dispersion composition.

<(B) The polymer compound represented by the above formula (1) having an acid value of less than 120 mgKOH/g>

In the present invention, the polymer compound (B) represented by the above formula (1) has an acid value of less than 120 mgKOH/g, preferably 100 mgKOH/g or less, more preferably less than 100 mgKOH/g. By setting it as the said range, the aggregation of the acid group of the polymer compound (B) can be prevented, and the phase separation between the metal oxide particle (A) and the polymer compound (B) can be prevented. As a result, the coated surface can be made good.

In addition, the lower limit of the acid value is not particularly limited, but is preferably 5 mgKOH/g or more, and more preferably 10 mgKOH/g or more from the viewpoint of dispersion stability of the metal oxide particles.

In addition, when the cured film is formed, the acid value of the polymer compound (B) is particularly preferably from 70 mgKOH/g to 90 mgKOH/g.

Here, the acid value of the polymer compound (B) is the solid component acid value of the polymer compound (B).

In the present invention, the acid value of the polymer compound (B) can be calculated, for example, from the average content of the acid groups in the polymer compound (B). The acid value of the polymer compound (B) can be adjusted by appropriately adjusting the amount of the acid group in the polymer compound (B) and the amount of the functional group having a pKa of 5 or more. For example, when the polymer compound (B) is synthesized, the amount of the compound having an acid group and a carbon-carbon double bond, which is a raw material, and a functional group having a pKa of 5 or more and a carbon-carbon double bond can be appropriately adjusted. The polymer compound (B) having a desired acid value is synthesized by adding the compound and the amount of the vinyl monomer having an acid group.

Hereinafter, each group in the above formula (1) will be described in detail.

The above A ¹ represents a monovalent organic group containing at least one functional group or a structure such as an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, and a coordination group. a radical of a oxygen atom, a phenol group, an alkyl group, an aryl group, a group having an alkylene oxide chain, a quinone imine group, an alkoxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, a functional group having an adsorption capacity for metal oxide particles (A) like an alkoxyalkyl group, an epoxy group, an isocyanate group or a hydroxyl group, and the above structure may have a metal oxide particle (A) as a heterocyclic ring structure The structure of the adsorption capacity.

In the following, the portion (the functional group and the structure) having the ability to adsorb the metal oxide particles (A) is collectively referred to as an "adsorption site".

It suffices to contain at least one adsorption site in one A ¹ , and it may contain two or more.

The form in which two or more adsorption sites are contained in one A ¹ may be a chain-like saturated hydrocarbon group (which may be linear or branched, preferably has a carbon number of 1 to 10) and a ring shape. a saturated hydrocarbon group (preferably having a carbon number of 3 to 10), an aromatic group (preferably having a carbon number of 5 to 10, for example, a phenyl group), and bonding two or more adsorption sites to form a monovalent substituent The form of A ^{1 or} the like is preferably a form in which two or more adsorption sites are bonded via a chain-like saturated hydrocarbon group to form a monovalent substituent A ¹ .

Further, when the adsorption site itself constitutes a monovalent substituent, the adsorption site itself may be a monovalent substituent represented by A ¹ .

First, the adsorption site constituting the above A ¹ will be described below.

Examples of the "acid group" include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, a phosphonic acid group, a phosphinic acid group, and a boronic acid group. More preferably, it is more preferably a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, a phosphonic acid group, a phosphinic acid group, and more preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, or the like. A phosphonic acid group, particularly preferably a carboxylic acid group.

Examples of the "ureido group" include -NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein, R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 6). The above aryl group or an aralkyl group having 7 or more carbon atoms is preferable, and more preferably -NR ¹⁵ CONHR ¹⁷ (here, R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom or have a carbon number of 1) An alkyl group of ~10, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and particularly preferably -NHCONHR ¹⁷ (here, R ¹⁷ represents a hydrogen atom or a carbon number of 1 to 10) An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms).

Examples of the "urethane group" include -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ²¹ , and -OCONR ²² R ²³ (here, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R). ²² and R ²³ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms, and the like, and more preferably -NHCOOR ¹⁸ -OCONHR ²¹ (wherein, R ¹⁸ and R ²¹ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms), etc., particularly preferably -NHCOOR ¹⁸ and -OCONHR ²¹ (wherein, R ¹⁸ and R ²¹ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms) .

Examples of the "base having a coordinating oxygen atom" include an acetonitrile acetone group and a crown ether.

Examples of the "base having a basic nitrogen atom" include an amine group (-NH ₂ ) and a substituted imido group (-NHR ⁸ and -NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ and R ¹⁰ respectively The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 or more carbon atoms, and the aralkyl group having 7 or more carbon atoms, and the fluorenyl group represented by the following formula (a1) are represented by the following formula: The sulfhydryl group or the like represented by (a2) is a preferred example.

In the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

More preferably, it is an amine group (-NH ₂ ) or a substituted imido group (-NHR ⁸ , -NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ and R ¹⁰ each independently represent a carbon number of 1 ～10 alkyl group, phenyl group, benzyl group), fluorenyl group represented by the above formula (a1). In the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms. Phenyl group, benzyl group, and fluorenyl group represented by the above formula (a2). In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group] Wait.

In particular, an amine group (-NH ₂ ) or a substituted imido group (-NHR ⁸ , -NR ⁹ R ¹⁰ may be preferably used, wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent a carbon number of 1~ An alkyl group, a phenyl group or a benzyl group of 5, and a fluorenyl group represented by the above formula (a1). In the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 5 carbon atoms and benzene. a benzyl group represented by the above formula (a2), wherein R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group, etc. .

The alkyl group represented by the above-mentioned monovalent substituent A ¹ may be linear or branched, preferably an alkyl group having 1 to 40 carbon atoms, more preferably 4 to 30 carbon atoms. The alkyl group is more preferably an alkyl group having a carbon number of 10 to 18.

The aryl group represented by the above monovalent substituent A ¹ is preferably an aryl group having 6 to 10 carbon atoms.

As the "group having an alkylene oxide chain", an alkoxy group is preferably formed at the terminal end, and more preferably an alkoxy group having a carbon number of 1 to 20 is formed. Further, the alkylene oxide chain is not particularly limited as long as it has at least one alkyleneoxy group, but preferably contains an alkyleneoxy group having 1 to 6 carbon atoms. Examples of the alkyleneoxy group include -CH ₂ CH ₂ O-, -CH ₂ CH ₂ CH ₂ O-, and the like.

The alkyl group in the above "alkoxycarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms.

The alkyl group in the above "alkylaminocarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the "carboxylate group" include a group containing an ammonium salt of a carboxylic acid.

As the "sulfonamide group", a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (methyl group, etc.), a mercapto group (ethyl fluorenyl group, a trifluoroethyl group, or the like).

Examples of the "heterocyclic structure" include thiophene, furan, dibenzopyran, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazole, and imidazole. , oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindole Preferred examples are porphyrin, isoindolinone, benzimidazolone, benzothiazole, carbendazim, hydrazine, quinoline, oxazole, acridine, acridone and hydrazine.

Examples of the above "indenylene group" include amber imine, phthalimide, naphthyl imine, and the like.

In addition, the "heterocyclic structure" and the "indenylene group" may further have a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a phenyl group. a naphthyl group having a carbon number of 6 to 16 such as an aryl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylamino group, an ethoxy group, and the like, and a decyloxy group having 1 to 6 carbon atoms. An alkoxy group having 1 to 20 carbon atoms such as a methoxy group or an ethoxy group; a halogen atom such as chlorine or bromine; an alkane having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; A carbonate group such as an oxycarbonyl group, a cyano group or a third butyl carbonate.

The above "alkoxyalkylene group" may be any of a monoalkoxyalkyl group, a dialkoxyalkyl group or a trialkoxyalkyl group, and is preferably a trialkoxyalkyl group. Trimethoxydecyl, triethoxydecyl, and the like.

Examples of the above "epoxy group" include a substituted or unsubstituted oxirane group (ethylene oxide group).

In particular, when the acid value of the polymer compound (B) is less than 120 mgKOH/g, the coating surface is good, and the interaction with the metal oxide particles (A) is good, A ^{1 is} preferably a monovalent substituent containing at least one functional group having a pKa of 5 or more, and more preferably a monovalent substituent containing at least one functional group having a pKa of 5 to 14.

The "pKa" as used herein refers to the pKa defined in Chemical Handbook (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.).

Examples of the functional group having a pKa of 5 or more include a coordinating oxygenogen. a group having a basic nitrogen atom, a phenol group, a ureido group, a urethane group, an alkyl group, an aryl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, a group having an alkylene chain , quinone imine group, carboxylate group, sulfonamide group, hydroxyl group, heterocyclic group and the like.

Specific examples of the functional group having a pKa of 5 or more include a phenol group (pKa of about 8 to 10), an alkyl group (pKa of about 46 to 53), and an aryl group (pKa of about 40 to 43). Urea group (pKa is about 12 to 14), urethane group (pKa is about 11 to 13), -COCH ₂ CO- as a coordinating oxygen atom (pKa is about 8 to 10), sulfonamide The base (pKa is about 9 to 11), the hydroxyl group (pKa is about 15 to 17), and the heterocyclic group (pKa is about 12 to 30).

Among the above, as the above A ¹ , it is preferred to contain at least one selected from the group consisting of an acid group, a phenol group, an alkyl group, an aryl group, a group having an alkylene oxide chain, a hydroxyl group, a urea group, and a urethane group. a monovalent substituent of a group in the group consisting of a sulfonamide group, a sulfonium imino group, and a group having a coordinating oxygen atom.

In the above formula (1), R ² represents a single bond or a divalent linking group. The n R ^{2 's} may be the same or different.

The divalent linking group represented by R ² includes one to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 hydrogen atoms. And a group of 0 to 20 sulfur atoms may be unsubstituted or further have a substituent.

R ^{2 is} preferably a single bond, or from 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0. A divalent linking group composed of ~5 sulfur atoms.

R ^{2 is more} preferably selected from a chain-like saturated hydrocarbon group (which may be linear or branched, preferably having a carbon number of 1 to 20) and a cyclic saturated hydrocarbon group (preferably having a carbon number of 3 to 3). 20) a group in the group consisting of an aromatic group (preferably having a carbon number of 5 to 20, for example, a phenyl group), a thioether bond, an ester bond, a guanamine bond, an ether bond, a nitrogen atom, and a carbonyl group. Or a combination of two or more of these groups, more preferably selected from the group consisting of a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, a thioether bond, an ester bond, an ether bond, and a guanamine bond. The group in the group formed, or a group in which two or more of the groups are combined, particularly preferably selected from the group consisting of a chain saturated hydrocarbon group, a thioether bond, an ester bond, an ether bond, and a guanamine bond. A group in a group, or a group in which two or more of these groups are combined.

In the above, when the divalent linking group represented by R ² has a substituent, examples of the substituent include an alkyl group having a carbon number of 1 to 20 such as a methyl group or an ethyl group, and a phenyl group or a naphthalene group. An aryl group having a carbon number of from 1 to 6 such as an aryl group having 6 to 16 carbon atoms, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonyl decylamino group, an ethoxycarbonyl group, and the like An alkoxy group having 1 to 6 carbon atoms such as an oxy group or an ethoxy group; a halogen atom such as chlorine or bromine; an alkoxy group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; A carbonate group such as a carbonyl group, a cyano group or a third butyl carbonate.

In the above formula (1), R ¹ represents a (m+n)-valent linking group. m+n satisfies 3~10.

The (m+n)-valent linking group represented by R ¹ includes one to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to A group consisting of 200 hydrogen atoms and 0 to 20 sulfur atoms may be unsubstituted or may have a substituent.

The (m+n)-valent linking group represented by R ¹ is preferably a group represented by any one of the following formulae.

In the above formula, L ₃ represents a trivalent group. T ₃ represents a single bond or a divalent linking group, and three T ₃ groups may be the same or different.

L ₄ represents a tetravalent group. T ₄ represents a single bond or a divalent linking group, and four T ₄ groups may be the same or different.

L ₅ represents a pentavalent group. T ₅ represents a single bond or a divalent linking group, and five of T ₅ may be the same or different.

L ₆ represents a hexavalent group. T ₆ represents a single bond or a divalent linking group, and six T ₆ groups may be the same or different.

Specific examples of the (m+n)-valent linking group represented by R ¹ described above are shown below (specific examples (1) to specific examples (17)). However, in the present invention, it is not limited by these specific examples.

In the above specific examples, the optimum (m+n) valent linking group is the following (1), (2) from the viewpoints of availability of raw materials, easiness of synthesis, and solubility in various solvents. , (10), (11), (16), (17).

In the above formula (1), m represents a positive number of 8 or less. The m is preferably 0.5 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.

Further, in the above formula (1), n represents 1 to 9. As n, it is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

In the above formula (1), P ¹ represents a polymer chain, and can be selected from known polymers and the like according to the purpose and the like. m P ^{1 's} may be the same or different.

Among the polymers, when a polymer chain is to be formed, it is preferably selected from a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, a guanamine. a polymer, an epoxy polymer, an anthrone polymer, and a modified or copolymer thereof [for example, a polymer comprising a polyether/polyurethane copolymer, a polyether/vinyl monomer) At least one of the group consisting of a copolymer or the like (which may be any of a random copolymer, a block copolymer, and a graft copolymer), more preferably selected from a polymer of a vinyl monomer or a copolymer, an ester polymer, an ether polymer, a urethane polymer, and a modified or copolymer thereof At least one type, particularly preferably a polymer or copolymer of a vinyl monomer.

The polymer or copolymer, the ester polymer, and the ether polymer which may be a vinyl monomer which the polymer chain P ^{1 has} may preferably have the following general formula (L), general formula (M), The structure represented by the formula (N).

In the above formula, X ¹ represents a hydrogen atom or a monovalent organic group. From the viewpoint of the restriction on the synthesis, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferred, and a hydrogen atom or a methyl group is more preferred, and a methyl group is particularly preferred.

R ¹⁰ represents a hydrogen atom or a monovalent organic group, and is not particularly limited in structure, but is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ¹⁰ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a carbon number of 5 to 20 The cyclic alkyl group is more preferably a linear alkyl group having 1 to 20 carbon atoms, particularly preferably a linear alkyl group having 1 to 6 carbon atoms. In the general formula (L), R ¹⁰ having two or more different structures may be used.

R ¹¹ and R ¹² represent a branched or linear alkyl group (the number of carbon atoms is preferably from 1 to 10, more preferably from 2 to 8, more preferably from 3 to 6). There may be two or more kinds of structurally different R ¹¹ or R ¹² in each formula.

K1, k2, and k3 each independently represent the number of 5 to 140.

The polymer chain P ¹ preferably contains at least one repeating unit.

The number k of repetitions of the at least one repeating unit in the polymer chain P ¹ is preferably 3 or more, and more preferably 5 or more, from the viewpoint of exerting the steric repulsive force and improving the dispersibility.

In addition, from the viewpoint of suppressing an increase in the volume of the polymer compound (B) and causing the metal oxide particles (A) to closely exist in the cured film (transparent film) and achieving a high refractive index, the at least one kind of repetition The number k of repeating units of the unit is preferably 60 or less, more preferably 40 or less, still more preferably 30 or less.

Further, the above polymer is preferably soluble in an organic solvent. When the affinity with an organic solvent is low, affinity with a dispersion medium may become weak, and the adsorption layer which is sufficient for the dispersion stabilization may not be securable.

The vinyl monomer is not particularly limited, and is preferably, for example, a (meth) acrylate, a crotonate, a vinyl ester, a vinyl monomer having an acid group, or a maleic acid diester. Class, fumaric acid diester, itaconic acid diester, (meth) acrylamide, styrene, vinyl ether, vinyl ketone, olefin, maleicene An amine, (meth)acrylonitrile or the like, more preferably a (meth) acrylate, a crotonate, a vinyl ester, a vinyl monomer having an acid group, and even more preferably a (meth)acrylic acid. Esters, crotonates.

As preferred examples of the vinyl monomers, the paragraphs in the specification of the Japanese Patent Application Publication No. 2007-277514, paragraphs 0089 to 0094, paragraph 0096, and paragraph 0097 (the corresponding US Patent Application Publication No. 2010/233595) The vinyl monomers described in 0105~Paragraph 0117, and Paragraph 0119~Paragraph 0120), which may be incorporated into the specification of the present application.

In addition to the above compounds, for example, a vinyl monomer having a functional group such as a urethane group, a ureido group, a sulfonylamino group, a phenol group or a quinone group can also be used. As such a monomeric substance having a urethane group or a ureido group, for example, an addition reaction of an isocyanate group with a hydroxyl group or an amine group can be suitably carried out. Specifically, an addition reaction of a monomer containing an isocyanate group with a compound containing one hydroxyl group, or a compound containing one primary amino group or a secondary amino group, or a monomer having a hydroxyl group, or The addition reaction of a monomer containing a primary amino group or a secondary amine group with a monoisocyanate is suitable for synthesis.

Among the polymer compounds (B) represented by the above formula (1), a polymer compound represented by the following formula (2) is preferred.

In the above formula (2), the meaning of A ^{2 is} the same as the above A ¹ in the above formula (1), and the preferred embodiment is also the same.

In the above formula (2), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group. The n R ^{4 's} may be the same or different. In addition, m R ^{5 's} may be the same or different.

The divalent linking group represented by R ⁴ and R ⁵ may be the same as the divalent linking group exemplified as the divalent linking group represented by R ^{2 of} the above formula (1). The best form is the same.

In particular, the divalent linking group represented by R ⁴ and R ⁵ is preferably selected from a chain-like saturated hydrocarbon group (which may be linear or branched, preferably having a carbon number of 1 to 20). a cyclic saturated hydrocarbon group (preferably having a carbon number of 3 to 20), an aromatic group (preferably having a carbon number of 5 to 20, for example, a phenyl group), an ester bond, a guanamine bond, an ether bond, a nitrogen atom, And a group in which a group consisting of a carbonyl group or a combination of two or more of these groups is more preferably selected from a chain-like saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, an ester bond, or an ether bond. And a group in the group consisting of a guanamine bond or a group in which two or more of the groups are combined, and more preferably selected from the group consisting of a chain saturated hydrocarbon group, an ester bond, an ether bond, and a guanamine bond. A group in the group formed, or a group in which two or more of the groups are combined.

In the above formula (2), R ³ represents a (m+n)-valent linking group. m+n satisfies 3~10.

The (m+n)-valent linking group represented by the above R ³ may be unsubstituted or may have a substituent, and may be used as (m+ represented by R ^{1 of} the above formula (1)). n) The linking group of the (m+n) valence listed in the valence linking group is the same, and the preferred embodiment is also the same.

In the above formula (2), m and n have the same meanings as m and n in the above formula (1), and preferred embodiments are also the same.

Further, P ² in the formula (2) has the same meaning as P ¹ in the above formula (1), and preferred embodiments are also the same. m P ^{2 's} may be the same or different.

Among the polymer compounds represented by the above formula (2), R ³ , R ⁴ , R ⁵ , P ² , m and n which are shown below are preferably satisfied.

R ³ : the above specific example (1), specific example (2), specific example (10), specific example (11), specific example (16) or specific example (17)

R ⁴ : a single bond, or a group selected from the group consisting of a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic group, an ester bond, a guanamine bond, an ether bond, a nitrogen atom, and a carbonyl group, or Base of two or more bases

R ⁵ : single bond, ethyl group, propyl group, the following group (a) or the following group (b)

Further, in the following group, R ¹² represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, and the modified product thereof

m:1~3

n: 3~6

In the polymer compound (B) represented by the above formula (1) or (2), it is more preferably from the viewpoint of dispersion stability, coating surface shape, and the like. A polymer compound represented by the formula (5).

In the above formula (5), R ⁶ represents a (m+n1+n2)-valent linking group, and R ⁷ to R ⁹ each independently represent a single bond or a divalent linking group.

A ³ represents a monovalent substituent containing at least one acid group. A ⁴ represents a monovalent substituent different from A ³ . The n1 A ³ and R ⁷ may be the same or different. N2 A ⁴ and R ⁸ may be the same or different.

The meaning of m is the same as m in the above formula (1), and the preferred embodiment is also the same. N1 represents 1~8, n2 represents 1~8, and m+n1+n2 satisfies 3~10.

P ^{3 has} the same meaning as P ² in the above formula (2), and the preferred embodiment is also the same. m P ³ and R ⁹ may be the same or different.

As the linking group of (m+n1+n2) valence related to R ⁶ , (m+n) which is represented by R ^{1 of the} above formula (1) or R ^{3 of} the above formula (2) can be used. The preferred linking forms are the same for the linking groups listed in the linking group of the valence.

The divalent linking group related to R ⁷ to R ⁹ may be the same as the divalent linking group exemplified as the divalent linking group represented by R ⁴ and R ^{5 in} the above formula (2). The preferred form is also the same.

Specific examples and preferred examples of the acid group which the substituent A ³ may have are the same as those of the specific examples and preferred examples described above for the acid group in the above formula (1).

More preferably above substituents A ³ is a divalent containing at least one acidic group having a pKa below 5 substituents, particularly preferably containing at least one selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, phosphonic acid group and a secondary The monovalent substituent of the group in the group consisting of phosphonic acid groups is preferably a carboxylic acid group.

Specific examples and preferred examples of the monovalent substituent A ⁴ different from A ³ may be other than the acid groups in the specific examples and preferred examples described above for A ^{1 in} the above formula (1). The same as the base. In particular, the substituent A ^{4 is} preferably a monovalent substituent containing at least one functional group having a pKa of 5 or more, and more preferably contains at least one selected from a group having a coordinating oxygen atom and having an alkalinity. a nitrogen atom group, a phenol group, a urea group, a urethane group, an alkyl group, an aryl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, a group having an alkylene oxide chain, a quinone imine group, a carboxy group a monovalent substituent of a group in the group consisting of an acid salt group, a sulfonylamino group, a hydroxyl group, and a heterocyclic group, particularly preferably an alkyl group, an aryl group, a group having a coordinating oxygen atom, and an alkali group A radical, ureido or urethane group of a nitrogen atom.

Examples of the substituent group A ³ in combination with the substituent group A ^4, A is preferably ³ above substituents containing at least one kind of functional group a pKa less than 5, a monovalent substituent, and said substituent group containing at least one A ⁴ A monovalent substituent having a pKa of 5 or more.

More preferably, the above substituent A ³ is a monovalent substituent containing at least one group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and a phosphinic acid group, and a ⁴ above substituents containing at least one selected from the group consisting of an oxygen atom having a coordinating group, a group having a basic nitrogen atom, a phenol group, a ureido group, a urethane group, an alkyl group, an aryl group, an alkoxy Monovalent group of groups in the group consisting of a carbonyl group, an alkylaminocarbonyl group, a group having an alkylene chain, a quinone imine group, a carboxylate group, a sulfonylamino group, a hydroxyl group and a heterocyclic group Substituent.

More preferably, the substituent A ³ is a monovalent substituent having a carboxylic acid group, and the substituent A ⁴ is an alkyl group, an aryl group, a group having a coordinating oxygen atom, and a group having a basic nitrogen atom. , ureido or urethane groups.

From the viewpoint of good adsorption of the metal oxide particles (A) (particularly, titanium dioxide particles) and the alkyl group of the substituent A ³ described later, it is particularly preferred that the substituent A ³ is a carboxylic acid group, and the above substitution The group A ⁴ is an alkyl group.

It is presumed that the adsorption of the titanium oxide particles and the alkyl group of the substituent A ⁴ is good because the alkyl group of the stearic acid and the alkyl group of the substituent A ⁴ are mutually reacted when the titanium oxide particles are surface-treated with stearic acid or the like. effect.

The molecular weight of the polymer compound (B) is preferably from 1,000 to 50,000, more preferably from 3,000 to 30,000, particularly preferably from 3,000 to 20,000, based on the weight average molecular weight. When the weight average molecular weight is within the above range, the effects of the plurality of adsorption sites introduced into the terminal of the polymer are sufficiently exhibited, and the properties excellent in the adsorptivity to the surface of the metal oxide fine particles can be exhibited.

As described later, when the cured film is formed, the visible light transmittance of the cured film is particularly excellent, and the weight average molecular weight of the polymer compound (B) is particularly preferably from 5,000 to 8,000.

(Synthesis method of polymer compound (B))

The polymer compound represented by the above formula (1) or (2) is not particularly limited, and can be as described in paragraphs 0114 to 0140 and paragraphs 0266 to 0348 of JP-A-2007-277514. Synthetic methods to synthesize.

In particular, it is preferred to synthesize the monomer represented by the above formula (1) or formula (2) by a method of radically polymerizing a vinyl monomer in the presence of a thiol compound having a plurality of adsorption sites. Polymer compound (B).

Only one type of the above vinyl monomers may be polymerized, or two or more types may be used in combination.

Here, preferred specific examples (M-1) to specific examples (M-9) and specific examples (M-14) to specific examples (M-16) of the vinyl monomer are shown below, but the present invention is not Limited to these specific examples.

More specifically, the method for synthesizing the polymer compound (B) represented by the above formula (1) or (2) is preferably in the presence of a compound represented by the following formula (3). A method of subjecting a vinyl monomer to radical polymerization.

In the above formula (3), R ⁶ , R ⁷ , A ³ , m, and n have the same meanings as R ³ , R ⁴ , A ² , m, and n in the above formula (2), respectively. The best form is the same.

In addition, as a method for synthesizing the polymer compound (B) represented by the above formula (1) or (2), the compound represented by the above formula (3) and the compound having a carbon-carbon double bond are large. A method of adding a molecular monomer (thiol-ene reaction method) is also preferred. As the catalyst for the reaction, a radical generator or a base is preferably used.

Specific examples of the macromonomer having a carbon-carbon double bond are shown below, but the present invention is not limited to these specific examples. In the following specific examples, the number of repeating units k is an integer of 3 to 50.

In addition, as a high score represented by the above formula (1) or formula (2) In the method for synthesizing the sub-compound (B), a method of forming a thioester group by a dehydration condensation reaction of a compound represented by the above formula (3) with a polymer compound having a carboxylic acid group is also preferred.

Specific examples of the polymer compound having a carboxylic acid group are shown below, but the present invention is not limited to these specific examples. In the following specific examples, the number of repeating units k is an integer of 3 to 50.

In addition, the method of synthesizing the polymer compound (B) represented by the above formula (1) or (2) is a compound represented by the above formula (3) and a polymer having a leaving group. A method of nucleophilic substitution reaction of a compound to form a thioether group is also preferred. As the leaving group, a halogen such as iodine, bromine or chlorine, or a sulfonic acid ester such as a tosylate, a mesylate or a triflate is preferable.

Specific examples of the polymer compound having a leaving group are shown below, but the present invention is not limited to these specific examples. In the following specific examples, the number of repeating units k is an integer of 3 to 50.

The compound represented by the above formula (3) is preferably synthesized by the following method.

A method of subjecting a compound having 3 to 10 fluorenyl groups in one molecule to a compound having the above-mentioned adsorption site and having a carbon-carbon double bond reactive with a thiol group.

The above addition reaction is particularly preferably a radical addition reaction. Further, as the carbon-carbon double bond, a mono- or di-substituted vinyl group is more preferable from the viewpoint of reactivity with a mercapto group.

Specific examples of the compound having 3 to 10 fluorenyl groups in one molecule [specific examples (18) to specific examples (34)] include the following compounds.

Among the above, a particularly preferable compound is the following compound from the viewpoints of availability of raw materials, easiness of synthesis, and solubility in various solvents.

The above compounds are available as commercial products (for example, (33) is diquat Tetraol hexa(3- decyl propionate): manufactured by 堺Chemical Industry Co., Ltd.).

a compound having the above-mentioned adsorption site and having a carbon-carbon double bond (specifically, at least one selected from the group consisting of an acid group, a urea group, an urethane group, a group having a coordinating oxygen atom, and a base) a nitrogen atom group, a phenol group, an alkyl group, an aryl group, a group having an alkylene oxide chain, a quinone imine group, an alkoxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, The group in the group consisting of a heterocyclic group, an alkoxyalkyl group, an epoxy group, an isocyanate group and a hydroxyl group and having a carbon-carbon double bond is not particularly limited, and the following compounds can be mentioned.

The above-mentioned radical addition reaction product of "a compound having 3 to 10 fluorenyl groups in one molecule" and "a compound having the above-mentioned adsorption site and having a carbon-carbon double bond" can be obtained, for example, by the following method: "a compound having 3 to 10 thiol groups in one molecule" and "having the above-mentioned adsorption site and having a carbon-carbon double bond The compound is dissolved in a suitable solvent, and a radical generating agent is added thereto, and the addition method is carried out at about 50 ° C to 100 ° C (thiol-ene reaction method).

An example of a suitable solvent used in the above-described thiol-ene reaction method may correspond to "a compound having 3 to 10 fluorenyl groups in one molecule", "having the above-mentioned adsorption site, and having carbon-carbon". The solubility of the compound of the double bond and the "radical addition reaction product formed" is arbitrarily selected.

For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 2-ethylhexanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl Ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene. These solvents may be used in combination of two or more.

Further, as the radical generating agent, for example, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4'-dimethylvaleronitrile) can be used. , 2,2'-azobisisobutyric acid dimethyl ester [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], such as benzoic acid peroxide, as well as peroxide Potassium sulfate, ammonium persulfate-like persulfate, and the like.

The polymer compound of the present invention is preferably obtained by conventionally polymerizing the vinyl compound and the compound represented by the above formula (3) by a known method. In addition, the compound represented by the above formula (3) in the present invention functions as a chain transfer agent, and may be simply referred to as a "chain transfer agent" hereinafter.

For example, it can be obtained by using the following methods: The chain transfer agent is dissolved in a suitable solvent, and a radical polymerization initiator is added thereto to carry out polymerization in a solution at about 50 to 220 ° C (solution polymerization method).

An example of a suitable solvent used in the solution polymerization method can be arbitrarily selected in accordance with the solubility of the monomer to be used and the copolymer to be produced. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 2-ethylhexanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl Ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene. These solvents may be used in combination of two or more.

Further, as a radical polymerization initiator, for example, 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2,4'-dimethylvaleronitrile) can be used. , 2,2'-azobisisobutyric acid dimethyl ester [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], such as benzoic acid peroxide, as well as peroxide Potassium sulfate, ammonium persulfate-like persulfate, and the like.

In the dispersion composition of the present invention, the polymer compound (B) may be used alone or in combination of two or more.

The content of the polymer compound (B) based on the total solid content of the dispersion composition (or the curable composition described later) of the present invention is preferably from the viewpoints of dispersibility, high refractive index, and coating surface morphology. The range of 5 mass% to 40 mass% is more preferably in the range of 10% by mass to 35% by mass, and still more preferably in the range of 12% by mass to 30% by mass.

-Other dispersion resins -

In the dispersion composition of the present invention, the dispersibility of the metal oxide particles is adjusted For the purpose, the dispersion resin other than the specific resin described above (hereinafter sometimes referred to as "other dispersion resin") may be contained.

As another dispersion resin which can be used in the present invention, a polymer dispersant (for example, polyamine amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, and a modification) are mentioned. Polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formaldehyde condensate], and polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, Pigment derivatives and the like.

Other dispersion resins can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer depending on the structure thereof.

The other dispersion resin functions to prevent re-aggregation by being adsorbed on the surface of the metal oxide particles. Therefore, a terminal modified polymer having a fixed portion on the surface of the metal oxide particles, a graft polymer, and a block polymer are preferable.

On the other hand, other dispersion resins have an effect of promoting adsorption of the dispersion resin by modifying the surface of the metal oxide particles.

Specific examples of the other dispersion resin include "DISPERBYK101 (polymelamine phosphate), 107 (carboxylate), 110, 180 (copolymer containing acid group) manufactured by BYK Chemie. , 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", Evka ( EFKA4047, 4050, 4010, 4165 (polyurethane type), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polymerized) Esteramine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (anthocyanine derivative), 6750 (azo pigment derivative), Ajinomoto Fine-Chemistry "Ajisper PB821, PB822" manufactured by Techno), "Florene TG-710 (urethane oligomer)", "Polyflow No. 50E, No. 300 (acrylic copolymer) manufactured by Kyoeisha Chemical Co., Ltd. )", "Disparlon KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725 manufactured by Nanben Chemical Co., Ltd." "Demol RN, N (naphthalenesulfonic acid formaldehyde polycondensate), MS, C, SN-B (aromatic sulfonic acid formaldehyde polycondensate), "Homogenol L-18 (polymer polycarboxylic acid)) manufactured by Kao Corporation "Emalgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamin86 (stearylamine acetate)", "Solsperse 5000" by Lubrizol Derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type high score) ) ", Nikko Chemicals (Nikko Chemicals) manufactured" Nikol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "and the like.

In addition, as another dispersion resin, the following paragraph (0562) of the specification of the corresponding US Patent Application Publication No. 2012/235099 (the corresponding paragraph [0692] of the corresponding US Patent Application Publication No. 2012/235099) will be exemplified by the formula (ED). The compound (sometimes referred to as an ether dimer) is polymerized as a necessary monocomponent component, and the contents can be incorporated into the specification of the present application.

As a specific example of the ether dimer, reference can be made to Japanese Patent Laid-Open No. 2012-208494 The description of the ether dimer of the paragraph 0565 (corresponding to U.S. Patent Application Publication No. 2012/235099, the disclosure of which is incorporated herein by reference in its entirety in its entirety in its entirety in

Specific examples of the polymer obtained by polymerizing the compound represented by the formula (ED) as a necessary monocomponent component include the formula (ED) which will be described later in the binder polymer. Specific examples of the polymer obtained by polymerizing a compound as a necessary monocomponent component are the same.

These other resins may be used alone or in combination of two or more.

The dispersion composition of the present invention (or a curable composition to be described later) may contain another dispersion resin, or may contain no other dispersion resin, and when it contains another dispersion resin, the dispersion composition of the present invention (or a hardening composition described later) The content of the other dispersion resin of the total solid content of the material is preferably in the range of 1% by mass to 20% by mass, more preferably in the range of 1% by mass to 10% by mass.

<(C) Solvent>

The dispersion composition of the present invention contains a solvent, and the solvent can be constituted by using various organic solvents.

As the organic solvent usable herein, there are acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene. Alcohol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetamidine acetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Alcohol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl Azulene, γ-butyrolactone, methyl lactate, ethyl lactate, and the like.

These organic solvents may be used singly or in combination. The concentration of the solid component in the dispersion composition of the present invention is preferably from 2% by mass to 60% by mass.

The method for producing the dispersion composition of the present invention is not particularly limited, and a method for producing a dispersion composition which is generally used can be applied. For example, it can be produced by mixing the metal oxide particles (A), the polymer compound (B), and the solvent (C), and performing a dispersion treatment using a circulation type dispersing device (bead mill).

Furthermore, the present invention also relates to a method for producing the above-described dispersion composition, and to a method for producing the following curable composition.

<Sclerosing composition>

The curable composition of the present invention is preferably a curable composition comprising the above-described dispersion composition of the present invention and the polymerizable compound (D), optionally containing other components.

By forming the above-mentioned dispersion composition into a curable composition, a cured film (transparent film) having a high refractive index can be formed.

Further, the present invention relates to a transparent film formed using the curable composition of the present invention.

The refractive index of the cured film (the film formed by the curable composition and then the hardening reaction) obtained from the curable composition is preferably from 1.85 to 2.60, more preferably from 1.90 to 2.60.

The physical properties of the cured film having a refractive index of 1.85 to 2.60 can be suitably achieved by containing the polymer compound (B) in the curable composition of the present invention, and can also be achieved by any means, for example, by adjusting the polymerization. The type and content of the binder compound (D) or the binder polymer which can be further added, or the curable composition containing the metal oxide particles (A), and the type and content of the metal oxide particles are adjusted to be more reliably achieved.

In particular, by setting the metal oxide particles to the above preferred examples, the above physical properties can be preferably achieved.

Further, it is preferable that the composition of the present invention is a transparent composition, and more specifically, the composition of the present invention is a composition in which when a cured film having a film thickness of 1.0 μm is formed by a composition, The light transmittance in the thickness direction of the cured film is 90% or more over the entire wavelength region of 400 nm to 700 nm.

In other words, the transparent film of the present invention is a film having a light transmittance of 1.0 μm or more, and the light transmittance in the thickness direction of the film is 90% or more over the entire wavelength region of 400 nm to 700 nm.

When the curable composition contains the dispersion composition of the present invention or the polymerizable compound (D), the physical properties of such light transmittance can be achieved by any means, for example, by adjusting the polymerizable compound (D), or The type and content of the added binder polymer are suitably achieved. In addition, the physical properties of the light transmittance can be suitably achieved by adjusting the particle diameter of the metal oxide particles (A) or the type and amount of the polymer compound (B).

In particular, when a cured film is formed, the visible light transmittance of the cured film is particularly excellent. Preferably, the polymer compound (B) has a weight average molecular weight of 5,000 to 8,000, and preferably has an acid value of 70 mgKOH/g to 90 mgKOH/g, particularly preferably a weight average molecular weight of 5,000 to 8,000, and an acid. The value is 70 mgKOH/g to 90 mgKOH/g.

When the content of the metal oxide particles is large, the transparency of the cured film may become a problem. However, in the present invention, a cured film having excellent transparency can be obtained by using such a polymer compound (B).

In the curable composition and the transparent film of the present invention, in particular, in order to exhibit the desired characteristics of the undercoat film of the microlens or the color filter, the light transmittance is 90% over the entire wavelength region of 400 nm to 700 nm. The above is an important element.

The light transmittance is preferably 95% or more, more preferably 99% or more, and most preferably 100% over the entire wavelength region of 400 nm to 700 nm.

In view of the above, the curable composition of the present invention contains substantially no coloring agent (preferably, the content of the coloring agent is 0% by mass based on the total solid content of the composition).

(D) Polymeric compound

In the present invention, it is preferable to use "two or more epoxy groups or oxa groups in the molecule" from the viewpoint of solvent resistance of a cured film (transparent film) when producing a solid lens. A compound of a cyclobutyl group is referred to as a polymerizable compound (D).

a compound having two or more epoxy groups (oxiranyl groups) or oxetanyl groups in the molecule -

Specific examples of the compound having two or more epoxy groups in the molecule of the polymerizable compound (D) include a bisphenol A type epoxy resin and a bisphenol F type epoxy resin. A phenol novolac type epoxy resin, a cresol novolak type epoxy resin, an aliphatic epoxy resin, or the like.

These compounds are available as commercial products. For example, bisphenol A type epoxy resins are JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 ( Above, Mitsubishi Chemical (manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, manufactured by Di Ai Sheng (DIC) Co., Ltd.), etc., bisphenol F type epoxy resin is JER-806, JER-807, JER- 4004, JER-4005, JER-4007, JER-4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, manufactured by Di Aisheng (share)), LCE-21, RE-602S (above, Japanese) Pharmaceutical (manufacturing), etc., phenol novolac type epoxy resin is JER-152, JER-154, JER-157S70, JER-157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N- 770, EPICLON N-775 (above, manufactured by Di Aisheng (share)), etc., cresol novolak type epoxy resin is EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N- 680, EPICLON N-690, EPICLON N-695 (above, manufactured by Di Aisheng (share)), EOCN-1020 (above, manufactured by Nippon Chemical Co., Ltd.), etc., aliphatic epoxy resin is ADEKA RESIN EP-408 0S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above, manufactured by ADEKA), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE-3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above, Daicel (Daicel) Chemical industry (manufactured by the company), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, Nagase chemteX (manufactured by the company)). Other than this, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above, manufactured by Eddy Co., Ltd.), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by Eddie Co., Ltd.), JER-1031S (manufactured by Mitsubishi Chemical Corporation).

These compounds may be used alone or in combination of two or more.

Specific examples of the compound having two or more oxetanyl groups in the molecule include ARON OXETANE OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.).

Further, the oxetanyl group-containing compound is preferably used alone or in combination with an epoxy group-containing compound.

Further, as the (D) polymerizable compound, an addition polymerizable compound having at least one ethylenically unsaturated double bond may be used, and it is preferred to use at least one, preferably two or more terminal ethylenic groups. A compound that saturates the bond.

In the present invention, the polymerizable compound (D) is more preferably a compound selected from the group consisting of two or more epoxy groups or oxetanyl groups in the above molecule, and a compound having two or more terminal ethylenically unsaturated bonds. At least one of the group consisting of.

Such an addition polymerizable compound having at least one ethylenically unsaturated double bond is a compound widely known in the art, and these compounds can be used without particular limitation in the present invention.

When such a compound is used as the (D) polymerizable compound, the curable composition of the present invention preferably further contains a polymerization initiator (E) to be described later.

Such an addition polymerizable compound having at least one ethylenically unsaturated double bond has, for example, a monomer, a prepolymer, that is, a dimer, a trimer, and an oligomer, or a mixture thereof and copolymerization thereof. Chemical forms such as matter. Examples of the monomer and the copolymer thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, guanamines. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound are used. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group or an unsaturated carboxylic acid oxime amine may be suitably used, and a monofunctional or polyfunctional isocyanate or an epoxy compound may be used. A reactant, a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid, and the like. Further, an addition reaction of an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or an unsaturated carboxylic acid oxime amine with a monofunctional or polyfunctional alcohol, an amine or a thiol Further, an unsaturated carboxylic acid ester having a detachable substituent such as a halogen group or a tosyloxy group or an unsaturated carboxylic acid amide, and a monofunctional or polyfunctional alcohol, an amine or a thiol. Substituting the reactants is also suitable. Further, as another example, a compound group substituted with an unsaturated phosphonic acid, styrene, vinyl ether or the like may be used instead of the above unsaturated carboxylic acid. As the specific compound, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

Further, as (D) a polymerizable compound (hereinafter, also referred to as "poly" A conjugate monomer or the like, or a "polymerizable monomer", which has at least one vinyl group which can undergo addition polymerization, and which has an ethylenically unsaturated group having a boiling point of 100 ° C or higher at normal pressure good. Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol IV (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tri (propylene oxypropyl propyl) (meth)acrylic acid after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol, such as ether, tris(propylene methoxyethyl) isomeric cyanurate, glycerin or trimethylolethane The esterification of the (meth)acrylic acid urethanes as described in the Japanese Patent Publication No. Sho-48-41708, the Japanese Patent Publication No. Sho. Japanese Patent Laid-Open No. 48-64183, Japanese Patent Publication No. Sho 49-43191, and Japanese Patent Publication No. Sho 52-30490 Polyester acrylates described, epoxy acrylate as the epoxy polymer and (meth) acrylic acid reaction product of polyfunctional acrylate or methacrylate, and a mixture of these.

A polyfunctional (meth)acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group or an ethylenically unsaturated group such as glycidyl (meth)acrylate may, for example, be mentioned.

In addition, as another preferable polymerizable compound, Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, and Japanese A compound having an anthracene and having a difunctional or higher vinyl polymerizable group, which is described in Japanese Patent No. 4264216, and the like, is a cardo polymer.

Further, as a compound having a boiling point of 100 ° C or higher and having at least one ethylenically unsaturated group capable of undergoing addition polymerization under normal pressure, paragraph number [0254] to paragraph number of JP-A-2008-292970 The compounds described in [0257] are also suitable.

Further, as the polymerizable monomer, the compound described in the general formula (1) and the general formula (2) together with the specific examples thereof can be used as the above-mentioned polyfunctional alcohol in the above-mentioned Japanese Patent Publication No. Hei 10-62986. A compound obtained by adding (meth) acrylate to ethylene oxide or propylene oxide.

Further, the polymerizable monomer used in the present invention is represented by the general formula (MO-1) to the general formula (MO-6) described in paragraphs 0297 to 0300 of JP-A-2012-215806. Polymerizable monomers are also preferred.

Specific examples of the radical polymerizable monomer represented by the above formula (MO-1) to (MO-6) are described in paragraph 0248 to paragraph 0251 of JP-A-2007-269779. The recited compounds can also be suitably used in the present invention.

Among them, as the polymerizable monomer or the like, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320) are preferred. ; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercially available) The product is KAYARAD DPHA; Nippon Chemical Pharmaceutical Co., Ltd. (manufactured by the company), and the structure of the (meth)acrylonitrile group between ethylene glycol and propylene glycol residues, or diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available) The product is M-460; East Asian synthetic manufacturing). These oligomer types can also be used.

For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) or the like can be mentioned.

The polymerizable monomer or the like may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Therefore, as described above, as long as the ethylenic compound has an unreacted carboxyl group as in the case of a mixture, the ethylenic compound can be directly used, and if necessary, the hydroxyl group and the non-aromatic compound of the above-mentioned ethylenic compound can also be used. The carboxylic anhydride is reacted to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkyl group. Hexahydrophthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and it is preferred to react an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to have an acid. The polyfunctional monomer is particularly preferred in the ester, and the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, the Aronix series M-305, M-510, M-520, etc. which are polyacid-acid-modified acrylic oligomer manufactured by the East Asia Synthetic Co., Ltd. are mentioned, for example.

A preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mg-KOH/g to 40 mg-KOH/g, particularly preferably from 5 mg-KOH/g to 30 mg-KOH/g. When two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is necessary to adjust the acid value of the entire polyfunctional monomer to the above range. whole.

Further, as the polymerizable monomer or the like, a polyfunctional mono-weight having a modified structure of caprolactone described in paragraphs 0306 to 0313 of JP-A-2012-215806 can be used.

For example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are sold by Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, can be cited as such a polyfunctional monomer having a modified structure of caprolactone. .

In the present invention, the polyfunctional monolith having a modified structure of caprolactone may be used singly or in combination of two or more.

In addition, as the polymerizable monomer or the like in the present invention, the general formula (Z-4) or the general formula (Z-5) described in paragraphs 0314 to 0324 of JP-A-2012-215806 may be used. The compound represented.

Commercial products such as a polymerizable monomer represented by the general formula (Z-4) and the general formula (Z-5) include, for example, Sartomer Co., Ltd. as having four ethylene oxides. Base chain tetrafunctional acrylate SR-494, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, as having 3 out-of-strand butoxy chains Trifunctional acrylate TPA-330 and the like.

In addition, as a polymerizable monomer, Japanese Patent Publication No. Sho 48-41708, Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent Publication No. Hei 2-32293, and Japanese Patent Publication No. Hei 2-16765 The urethane amides described in the Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japan A urethane compound having an ethylene oxide skeleton described in Japanese Patent Publication No. 62-39418 is also suitable. In addition, an amine-based structure or a sulfide structure is described in the molecule as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. As the polymerizable monomer, an addition polymerizable monomer can obtain a curable composition having a very excellent photospeed.

Commercial products such as a polymerizable monomer include urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp Co., Ltd.), and UA-7200 (Xinzhongcun Chemical Co., Ltd.). Manufactured, DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Co., Ltd.).

As the polymerizable monomer or the like, a polyfunctional thiol compound having two or more mercapto groups (SH) in the same molecule as described in JP-A-2012-150468, paragraphs 0216 to 0220, can also be used.

Further, specific examples of the monomer of the aliphatic polyamine compound and the decylamine of the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methyl acrylamide, and 1,6-hexa Methyl bis-acrylamide, 1,6-hexamethylene bis-methyl acrylamide, diethylene triamine tripropylene decylamine, phthaldimethyl bis decyl decylamine, benzyl dimethyl methacryl Amidoxime and the like.

Examples of other preferred amide-based monomers include those having a cyclohexylene structure described in Japanese Patent Publication No. Sho 54-21726.

Further, a urethane produced by an addition reaction of an isocyanate and a hydroxyl group The addition of a polymerizable compound is also suitable. For example, the addition of a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-A-48-41708 can be added. A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule of a vinyl monomer having a hydroxyl group represented by the following formula (V).

In the following formula (V), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group.

H ₂ C=C(R ⁷ )COOCH ₂ CH(R ⁸ )OH Formula (V)

In addition, the urethane urethanes described in Japanese Patent Application Laid-Open No. Hei. No. Hei. A urethane-based urethane group described in Japanese Patent Publication No. Sho 62-39417, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 Compounds are also suitable. In addition, an amine-based structure or a sulfide structure is described in the molecule as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A curable compound is obtained, and a curable composition having a very excellent photospeed can be obtained.

Other examples include, for example, Japanese Patent Laid-Open No. 48-64183, Japanese Patent Publication No. Sho 49-43191, and Japanese Patent Publication No. Sho 52-30490. The polyester acrylates described above are polyfunctional acrylates or methacrylates such as epoxy acrylates obtained by reacting an epoxy resin with (meth)acrylic acid. Further, a specific unsaturated compound described in Japanese Patent Publication No. Sho 46-43946, Japanese Patent Publication No. Hei. No. Hei. A vinylphosphonic acid-based compound or the like described in Japanese Patent Publication No. 25493. Further, in some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 can be suitably used. Further, photocurable monomers and oligomers described in "Japan Next Society" vol. 20, No. 7, 300 pages - 308 (1984) can also be used.

Regarding the polymerizable compounds, the details of the method of use, the use alone or in combination, and the amount of addition can be arbitrarily set in combination with the final performance design of the curable composition. For example, it is selected according to the following points.

From the viewpoint of sensitivity, it is preferred that the structure has a large content of unsaturated groups per molecule, and in many cases, it is preferably a difunctional or higher. Further, in order to increase the strength of the cured film, it may be a trifunctional or higher compound, and further, a different functional number may be used in combination. A method of adjusting both sensitivity and strength is also effective for a compound of a different polymerizable group (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound).

Further, the compatibility of the other components (for example, a polymerization initiator, metal oxide particles, etc.) contained in the curable composition, the dispersibility, the selection of the polymerizable compound. The method of use is also an important factor. For example, compatibility may be improved by using a low-purity compound or by using two or more other components in combination. In addition, for The adhesion to a hard surface such as a substrate can be improved, and a specific structure can be selected.

The content of the (D) polymerizable compound is preferably in the range of 1% by mass to 40% by mass, more preferably in the range of 3% by mass to 35% by mass, even more preferably 5%, based on the total solid content of the curable composition. The range of mass %~30% by mass.

When it is in this range, it is preferable to not lower the refractive index and to have good hardenability.

The curable composition of the present invention preferably further contains at least one selected from the group consisting of a polymerization initiator (E) described below and a binder polymer.

(E) polymerization initiator

From the viewpoint of further improving the curability, the curable composition of the present invention preferably further contains a polymerization initiator.

As the polymerization initiator in the present invention, those which are described below as a polymerization initiator can be used.

The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known polymerization initiators.

In addition, in the viewpoint of improving the hardening in the exposure step by radiation irradiation, such as step (ii) and step (b) in the method of forming the microlens to be described later, for example, it is preferable to be in the ultraviolet region to the visible light. The line has a sense of radioactivity. Further, it may be an active agent which generates a living radical with a photo-excited sensitizer, and may also be an initiator which starts cationic polymerization corresponding to the type of the monomer.

Further, the polymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in a range of from about 300 nm to 800 nm (more preferably from 330 nm to 500 nm).

Examples of the polymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton or a oxadiazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, a hexaarylbiimidazole, or an anthracene derivative. An hydrazine compound, an organic peroxide, a sulfur compound, a ketone compound, an aromatic sulfonium salt, a ketoxime ether, an aminoacetophenone compound, a hydroxyacetophenone or the like.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include, for example, a compound described in Japanese Society of Chemical Society (Bull. Chem. Soc. Japan), 42, 2924 (1969), and British Patent No. 1,848,492. The compound described in the specification, the compound described in JP-A-53-133428, the compound described in the specification of German Patent No. 3337024, and the "J. Org. Chem." by FC Schaefer et al. The compound described in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in the specification of U.S. Patent No. 4,212,976 and the like.

Further, examples of the polymerization initiator other than the above include an acridine derivative (for example, 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane, etc.), N-benzene. Glycine and the like, polyhalogen compounds (for example, carbon tetrabromide, phenyltribromomethylhydrazine, phenyltrichloromethyl ketone, etc.), coumarins (for example, 3-(2-benzophenone) Furanyl)-7-diethyl Amino coumarin, 3-(2-benzofuranyl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidene-7-diethylamine coumarin, 3 -(2-methoxybenzimidyl)-7-diethylaminocoumarin, 3-(4-dimethylaminobenzimidyl)-7-diethylamine coumarin, 3, 3'-Carbonyl bis(5,7-di-n-propoxycoumarin), 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzylidene-7-A Oxycoumarin, 3-(2-furanyl)-7-diethylaminocoumarin, 3-(4-diethylaminocinnamate)-7-diethylaminocoumarin , 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzylidene-5,7-dipropoxycoumarin, 7-benzotriazol-2-yl Japanese Patent No. 5-19475, Japanese Patent Laid-Open No. Hei 7-271028, Japanese Patent Laid-Open Publication No. 2002-363206, Japanese Patent Laid-Open No. 2002-363207, and Japanese Patent Laid-Open Publication No. 2002 a coumarin compound or the like described in JP-A-2002-363209, or a fluorenylphosphine oxide (for example, bis(2,4,6-trimethylbenzylidene)- Phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl -pentylphenylphosphine oxide, LucirinTPO, etc.), metallocenes (eg bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole) -1-yl)-phenyl)titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1+)-hexafluorophosphate (1-), etc., Japanese Patent Laid-Open No. 53-133428 The compound described in the specification of the Japanese Patent Publication No. Sho 57-1819, the Japanese Patent Publication No. Sho 57-6096, and the specification of U.S. Patent No. 3,615,455.

Examples of the ketone compound include the compounds described in paragraph 0084 of JP-A-2011-252945, and the contents of these can be incorporated into the specification of the present application.

As the polymerization initiator, a hydroxyacetophenone compound can also be suitably used, An aminoacetophenone compound, and a mercaptophosphine compound. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a sulfhydryl phosphine oxide-based initiator described in Japanese Patent No. 42258899 can be used. .

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) which are commercially available products can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179, which is a wavelength of a long-wavelength source such as 365 nm or 405 nm, can be used. Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF Corporation) which is a commercially available product can be used.

As the polymerization initiator, a lanthanoid compound can also be suitably used. As a specific example of the oxime-based initiator, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and JP-A-2006-342166 can be used. The compound described.

As the ruthenium compound such as an anthracene derivative which can be suitably used as a polymerization initiator in the present invention, for example, 3-benzylideneoxyimidobutan-2-one and 3-ethyloxyimide can be cited. Butyral-2-one, 3-propoxy methoxyiminobutan-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-ethyloxyimino group- 1-phenylpropan-1-one, 2-benzylideneoxy Amino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-benzene Propane-1-one and the like.

As the oxime ester compound, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.) can be used. Sale. Further, the description of the polymerization initiator described in paragraphs 0092 to 0096 of JP-A-2012-113104 can be referred to, and the contents of the above can be incorporated into the specification of the present application. By using such an antimony compound, it is possible to provide a curable composition having high curing sensitivity and good developability. The above ruthenium compound is a compound described in paragraph 0030 of JP-A-2012-113104. The general formula is represented by the general formula (I) described in the first claim of Japanese Patent Laid-Open Publication No. 2012-113104, and more preferably the general formula (IA) described in the third paragraph of the patent application scope. For the presenter, reference may be made to the descriptions, and the contents of the contents may be incorporated into the specification of the present application. In addition, "British Chemical Society, JC Perkin II" (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, "Photopolymer Science" Journal of Photopolymer Science and Technology, 1995 (pp. 202-232, "Journal of Applied Polymer Science" (2012) pp. 725-731, Japanese Patent Laid-Open The compound described in Japanese Laid-Open Patent Publication No. 2000-66385, Japanese Patent Laid-Open No. 2000-80068, paragraph 0218 to paragraph 0281, Japanese Patent Laid-Open Publication No. 2004-534797, paragraph 0242 to paragraph 0251, and Japanese Patent Laid-Open No. 2006-342166 Public The compounds and the like described in the report.

Commercially available products such as IRGACURE-OXE01 (manufactured by BASF Corporation) and IRGACURE-OXE02 (manufactured by BASF Corporation) can be suitably used.

In addition, as the oxime ester compound other than the above, a compound described in Japanese Patent Laid-Open Publication No. 2009-519904, in which N is attached to the N-position of the carbazole, and a hetero substituent introduced into the diphenyl ketone moiety may be used. The compound described in the U.S. Patent No. 7,626,957, the compound of the Japanese Patent Publication No. 2010-15025, and the Japanese Patent Publication No. 2009-292039, and the International Patent Publication No. 2009-131189 The ketone-based compound described in Japanese Patent No. 7556910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, and a Japanese patent having an absorption maximum at 405 nm and having a good sensitivity to a g-ray source. The compound or the like described in JP-A-2009-221114.

Further, a cyclic ruthenium compound described in JP-A-2007-2320, and JP-A-2007-322744 can be suitably used. Among the cyclic ruthenium compounds, the cyclic ruthenium compound which is condensed in the carbazole dye described in Japanese Patent Laid-Open Publication No. 2010-185072, and the like, has high light absorbing property. It is preferable from the viewpoint of high sensitivity.

In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of the ruthenium compound, can be highly sensitive by regenerating the living radical from the polymerization inert radical, and can also be suitably used. Use.

Further, an anthracene compound having a specific substituent as shown in JP-A-2007-269779 or a ruthenium compound having a thioaryl group as shown in JP-A-2009-191061 may be mentioned.

As the oxime initiator, the general formula (OX-1) and the following can be referred to in paragraph 0513 of the Japanese Patent Application Publication No. 2012-208494 (corresponding to [0632] of the specification of the corresponding US Patent Application Publication No. 2012/235099). Description of the compound represented by the formula (OX-2) or the formula (OX-3), the contents of which can be incorporated into the specification of the present application.

Specific examples (PIox-1) to specific examples (PIox-13) of the ruthenium compound which can be suitably used are shown below, but the present invention is not limited to these specific examples.

The ruthenium compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a ruthenium compound having a high absorbance at 365 nm and 405 nm.

From the viewpoint of sensitivity, the cerium compound is at 365 nm or 405 nm. The light absorption coefficient is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and particularly preferably from 5,000 to 200,000.

The molar absorption coefficient of the compound can be determined by a known method. Specifically, for example, it is preferably an ultraviolet-visible spectrophotometer (Carry-5 spctrophotometer manufactured by Varian), and uses acetic acid B. The ester solvent was measured at a concentration of 0.01 g/L.

The polymerization initiator to be used in the invention may be used in combination of two or more kinds as needed.

The (E) polymerization initiator used in the curable composition of the present invention is preferably a trihalomethyltriazine compound, a benzyldimethylketal compound, or α- from the viewpoint of hardenability. a hydroxyketone compound, an α-aminoketone compound, a mercaptophosphine compound, a phosphine oxide compound, a metallocene compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a benzothiazole compound, a diphenylketone compound, Acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, or 3-aryl substituted coumarin compounds.

More preferably, it is a trihalomethyltriazine compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a diphenylketone compound, or a phenylethyl group. a ketone compound, particularly preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a diphenyl ketone compound .

In particular, when the curable composition of the present invention is placed on a color filter of a solid-state imaging device to form a microlens, it is required to form a fine shape in a sharp shape. The pattern is therefore important for developing the unexposed portion with hardenability and no residue. From this point of view, it is particularly preferred to use a ruthenium compound as a polymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging element, a stepper is used for exposure for hardening, but there is a case where the exposure machine is damaged by halogen, and it is required to add a polymerization initiator. Since the suppression is low, in consideration of these aspects, it is preferable to use a ruthenium compound as the (E) polymerization initiator when forming a fine pattern such as a solid-state image sensor.

The content of the (E) polymerization initiator contained in the curable composition of the present invention (the total content in the case of two or more kinds) is preferably 0.1% by mass or more, based on the total solid content of the curable composition. 40% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, still more preferably 1% by mass or more and 15% by mass or less. Within this range, good hardenability, good sensitivity, and pattern formation properties can be obtained.

Further, the curable composition of the present invention may further contain any of the components described in detail below, as needed.

[sensitizer]

The curable composition of the present invention may contain a sensitizer for the purpose of improving the radical generating efficiency of the (E) polymerization initiator and the long wavelength of the photosensitive wavelength.

As the sensitizer which can be used in the present invention, it is preferred to sensitize the above (E) polymerization initiator by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer include those belonging to the following compounds and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.

Regarding the above sensitizer, for example, Japanese Patent Laid-Open Publication No. 2010-106268 The paragraphs [0230] to [0253] are described in detail in the corresponding U.S. Patent Application Publication No. 2011/0124824 A1 [0253] to [0273], the contents of which are incorporated herein by reference. in.

The content of the sensitizer in the curable composition is preferably 0.1% by mass or more and 20% by mass or less, in terms of solid content, from the viewpoint of the light absorption efficiency in the deep portion and the decomposition efficiency of the initiator. It is preferably 0.5% by mass or more and 15% by mass or less.

The sensitizer may be used alone or in combination of two or more.

[common sensitizer]

The curable composition of the present invention further preferably contains a co-sensitizer.

In the present invention, the co-sensitizer further enhances the effect of the (E) polymerization initiator or the sensitizer on the actinic radiation or the inhibition of the oxygen barrier (D) polymerizable compound.

Regarding the above-mentioned co-sensitizer, for example, paragraph [0254] to paragraph [0257] of the Japanese Patent Application Laid-Open No. 2010-106268 (corresponding U.S. Patent Application Publication No. 2011/0124824 A1, the specification of [0274] to [0279] It is described in detail in the above, and the contents of the contents can be incorporated into the specification of the present application.

The co-sensitizer may be used alone or in combination of two or more.

From the viewpoint of increasing the curing rate by the balance between the polymerization growth rate and the chain transfer, the content of the total sensitizer is preferably 0.1% by mass or more and 30% based on the mass of the total solid content of the curable composition. The range of the mass% or less is more preferably 1% by mass or more and 25% by mass or less, and still more preferably 1.5% by mass or more and 20%. The range of mass % or less.

[Polymerization inhibitor]

In the present invention, in order to prevent unnecessary polymerization of a compound having a polymerizable ethylenically unsaturated double bond during or during the production of the curable composition, it is preferred to add a polymerization inhibitor.

Examples of the polymerization inhibitor which can be used in the present invention include compounds containing a phenolic hydroxyl group, N-oxide compounds, piperidine 1-oxyl radical compounds, pyrrolidine 1-oxy radical compounds, and N. - nitrosophenylhydroxylamines, diazo compounds, and cationic dyes, compounds containing sulfur groups, compounds containing nitro groups, transition metal compounds such as FeCl ₃ and CuCl ₂ .

With regard to the above-mentioned polymerization inhibitor, for example, paragraph [0259] to paragraph [0281] of the Japanese Patent Laid-Open Publication No. 2010-106268 (corresponding to US Patent Application Publication No. 2011/0124824A1, [0281] to [0298]) It is described in detail.

The polymerization inhibitor may be used alone or in combination of two or more.

The amount of the polymerization inhibitor to be added is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the (E) polymerization initiator. It is preferably in the range of 0.05 parts by mass or more and 5 parts by mass or less.

By setting the above range, the curing reaction in the non-image portion is sufficiently suppressed, and the curing reaction in the image portion is sufficiently promoted, and the image formation property and the sensitivity are improved.

[Binder Polymer]

The curable composition of the present invention is preferred from the viewpoint of improving film properties and the like. To further contain a binder polymer.

As the above binder polymer, a linear organic polymer is preferably used. As such a linear organic polymer, a known polymer can be used arbitrarily. It is preferred to carry out water development or weak alkaline water development, and therefore a linear organic polymer which is soluble or swellable to water or weakly alkaline water is selected. The linear organic polymer is selected for use not only as a film forming agent but also as a water, a weakly alkaline water or an organic solvent developing solution. For example, if a water-soluble organic polymer is used, water development can be performed. Examples of such a linear organic polymer include a radical polymer having a carboxylic acid group in a side chain. For example, Japanese Patent Laid-Open Publication No. SHO 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japan Patent Publication No. Sho 58-12577, Japanese Patent Publication No. Sho 54-25957, Japanese Patent Laid-Open No. Sho 54-92723, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048 In the publication, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group is subjected to homopolymerization or copolymerization of a monomer having an acid anhydride, and the acid anhydride unit is hydrolyzed or semi-esterified or semi-oximed. An aminated resin, an epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of the monomer having an acid anhydride include a monomer having an acid anhydride. Maleic anhydride or the like.

Further, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition to this, it is useful to add a cyclic acid anhydride to a polymer having a hydroxyl group.

In the present invention, when a copolymer is used as a binder polymer, As the compound to be copolymerized, other monomers than the monomers listed above may also be used. Examples of the other monomer include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, A An acrylate having an aliphatic hydroxyl group such as 3-hydroxypropyl acrylate or 4-hydroxybutyl methacrylate, and a methacrylate.

(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid - 2-chloroethyl ester, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-ene acrylate An alkyl acrylate such as propoxyethyl acrylate or propargyl acrylate.

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, methacrylic acid 2 -ethylhexyl ester, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, Vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate, etc. Alkyl methacrylate.

(4) Acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyl Ethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl-N- Phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N, N-diallyl acrylamide, N, N-diallyl methacrylamide, allyl propylene Acrylamide or methacrylamide such as guanamine or allyl methacrylamide.

(5) Ethylene vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and other ethylene Base ethers.

(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate.

(7) Styrene such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene or p-ethoxylated styrene.

(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, and the like.

(11) maleimide, N-propylene decyl acrylamide, N-acetyl methacrylamide, N-propyl methacrylamide, N-(p-chlorobenzoquinone An unsaturated quinone imine such as methacrylamide.

(12) A methacrylic monomer having a hetero atom bonded to the α-position. For example, the compounds described in each of the publications such as JP-A-2002-309057 and JP-A-2002-311569 can be cited.

In the present invention, the monomers can be applied to the synthesis of the copolymer by being combined without particular limitation within the scope of the present invention. For example, the following representation makes this An example of a copolymer obtained by polymerizing a monomer component of each monomer is not limited thereto. The composition ratio of the exemplified compounds shown below is mol%.

In the above-mentioned binder polymer, reference may be made to the formula (ED) which is represented by the formula (ED) after the paragraph 0562 of the Japanese Patent Application Laid-Open No. 2012-208494 (the corresponding [0692] of the U.S. Patent Application Publication No. 2012/235099). The description of a compound obtained by polymerizing a compound (sometimes referred to as an ether dimer) as an essential monomer component can be incorporated into the specification of the present application.

As a specific example of the ether dimer, reference is made to the description of the ether dimer of the Japanese Patent Application Laid-Open No. 2012-208494, No. 0565 (the corresponding US Patent Application Publication No. 2012/235099 [0694]), which is incorporated herein by reference. Some of the content can be incorporated into the specification of the present application.

In addition, specific examples of the polymer obtained by polymerizing the compound represented by the formula (ED) as a necessary monocomponent component are exemplified below, but the present invention is not limited to these specific examples. The composition ratio of the exemplified compounds shown below is mol%.

In the present invention, it is particularly preferred to use dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate (hereinafter referred to as "DM") or benzyl methacrylate (hereinafter referred to as Called "BzMA"), methyl methacrylate (hereinafter referred to as "MMA"), methacrylic acid (hereinafter referred to as "MAA"), and glycidyl methacrylate (hereinafter referred to as "GMA") are copolymerized. polymer. In particular, the molar ratio of DM:BzMA:MMA:MAA:GMA is preferably 5~15:40~50:5~15:5~15:20~30. It is preferable that 95% by mass or more of the components constituting the copolymer used in the present invention are these components. Further, the weight average molecular weight of the polymer is preferably from 9000 to 20,000.

The weight average molecular weight (polystyrene equivalent value measured by Gel Permeation Chromatography (GPC)) of the polymer used in the present invention is preferably from 1,000 to 2 × 10 ⁵ , more preferably 2000~1×10 ⁵ , and more preferably 5000~5×10 ⁴ .

Among these, a (meth)acrylic resin having an allyl group or a vinyl ester group and a carboxyl group in a side chain, and a method described in JP-A-2000-187322, JP-A-2002-62698 The alkali-soluble resin having a double bond in the side chain or the alkali-soluble resin having a guanamine group in the side chain described in JP-A-2001-242612 is excellent in balance of film strength, sensitivity, and developability. Suitable. Examples of the above polymer include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (polyurethane acrylic oligomer containing COOH. Diamond Shamrock). Co.Ltd., manufactured by Viscoat R-264, KS RESIST106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series such as Cyclomer P ACA230AA, and Placcel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.) ), Ebecryl3800 (大赛璐-UCB) (Manufactured by Daicel-UCB) Co., Ltd.).

In addition, Japanese Patent Laid-Open No. 7-120040, Japanese Patent Laid-Open No. 7-120041, Japanese Patent Laid-Open No. 7-120042, Japanese Patent Publication No. Hei 8-12424, and Japanese Patent Laid-Open No. 63-287944 The acid group-containing urethane-based adhesive polymer described in Japanese Laid-Open Patent Publication No. Hei No. No. Hei. No. Hei. No. Hei. The urethane-based binder polymer having an acid group and a double bond in the side chain described in the No. 107918 is excellent in strength, and is therefore advantageous from the viewpoint of film strength.

In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in the above-mentioned European Patent No. 993, 966, the European Patent No. PCT No. PCT No. 2001-318463, and the like, is also excellent in film strength. And appropriate.

Further, in addition to the above, as the water-soluble linear organic polymer, polyvinylpyrrolidone or polyethylene oxide is useful. Further, in order to increase the strength of the hardened film, alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin may also be useful.

The weight average molecular weight (polystyrene equivalent value measured by the GPC method) of the binder polymer which can be used for the curable composition of the present invention is preferably 5,000 or more, more preferably 10,000 or more, or 30. In the range of 10,000 or less, the number average molecular weight is preferably 1,000 or more, more preferably 2,000 or more and 250,000 or less. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.

The binder polymers may be random polymers, block polymers, graft polymerization Any kind of thing.

Adhesive polymers useful in the present invention can be synthesized by previously known methods. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and acetic acid 2. - methoxyethyl ester, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N , N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl hydrazine, water, and the like. These solvents may be used singly or in combination of two or more.

A known compound such as an azo initiator or a peroxide initiator can be used as the radical polymerization initiator to be used in the polymerization of the binder polymer in the curable composition of the present invention.

In the curable composition of the present invention, the binder polymer may be used singly or in combination of two or more kinds.

The curable composition of the present invention may contain a binder polymer or a binder polymer. When the binder polymer is contained, the binder polymer content is preferably relative to the total solid content of the curable composition. 1% by mass or more and 40% by mass or less, more preferably 3% by mass or more and 30% by mass or less, still more preferably 4% by mass or more and 20% by mass or less.

[Surfactant]

From the viewpoint of further improving the coatability, various curable agents may be added to the curable composition of the present invention. As the surfactant, a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, or an anionic interface can be used. Various surfactants such as an active agent and an anthrone-based surfactant.

In particular, the curable composition of the present invention further improves liquid characteristics (particularly fluidity) when it is prepared as a coating liquid by containing a fluorine-based surfactant, so that uniformity of coating thickness or liquid-saving can be further improved. Sex.

In other words, when a film is formed using a coating liquid to which a photosensitive transparent composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered, whereby the surface to be coated is wetted. The wettability is improved, and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is effective to form a film having a uniform thickness with a small thickness unevenness.

The fluorine content in the fluorine-based surfactant is suitably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, particularly preferably 7% by mass to 25% by mass. From the viewpoint of the uniformity of the thickness of the coating film or the liquid-saving property, the fluorine content is effective in the fluorine-based surfactant in the range, and the solubility in the curable composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F 142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, and Megafac F479. , Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, manufactured by Di Ai Sheng (share)), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, Sumitomo 3M (share)), Surflon S-382 , Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA).

Specific examples of the non-ionic surfactants include those described in JP-A-2012-208494, paragraph 0553 (corresponding to US Patent Application Publication No. 2012/0235099 [0679]). Ionic surfactants, the contents of which can be incorporated into the specification of the present application.

The cation-based interface described in JP-A-2012-208494, paragraph 0554 (corresponding to US Patent Application Publication No. 2012/0235099 [0680]), the cation-based interface is exemplified. Active agents, the contents of which can be incorporated into the specification of the present application.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

Examples of the anthrone-based surfactant include Toray. "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone SH11PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Toray" manufactured by Dow Corning (share) Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" manufactured by Momentive Performance Materials, Shin-Etsu "KP341", "KF6001", "KF6002" manufactured by Shinetsu Silicon Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by BYK Chemical Co., Ltd., etc.

The surfactant may be used alone or in combination of two or more.

The curable composition may contain a surfactant or may not contain a surfactant. When the surfactant is contained, the amount of the surfactant added is preferably 0.001% by mass to 2.0% by mass based on the total mass of the curable composition. More preferably, it is 0.005 mass% to 1.0 mass%.

[Other additives]

Further, in order to improve the physical properties of the cured film, a known additive such as a plasticizer or a lipid-sensitive agent may be added to the curable composition.

The other additives may be used alone or in combination of two or more.

As the plasticizer, for example, dioctyl phthalate, di-dodecyl phthalate, triethylene glycol dioctanoate, dimethyl glycol phthalate, tricresyl phosphate , dioctyl adipate, dibutyl sebacate, triethylene glyceryl, etc., when a binder polymer is used, 10% by mass can be added to the total mass of the polymerizable compound and the binder polymer. the following.

[UV absorber]

The curable composition of the present invention may also contain an ultraviolet absorber. As the ultraviolet absorber, a compound represented by the following formula (I) which is a conjugated diene compound is particularly preferable.

In the above formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² are each other. They may be the same or different, but do not simultaneously represent a hydrogen atom.

Further, R ¹ and R ² may form a cyclic amino group with the nitrogen atom R ¹ and R ² are bonded together. Examples of the cyclic amino group include a piperidinyl group, a morpholinyl group, a pyrrolidinyl group, a hexahydroaza group, and a piperazinyl group.

In the above formula (I), R ³ and R ⁴ represent an electron withdrawing group. Herein, the electron withdrawing group is a Hammett substituent constant σ _p value (hereinafter referred to as "σ _p value" is) is 0.20 or more and 1.0 or less electron-withdrawing group. Preferably, the σ _p value is 0.30 or more and 0.8 or less.

The Hammett's rule is to quantitatively discuss the effects of substituents on the reaction or balance of benzene derivatives, and the rule of thumb advocated by LP Hammett in 1935 is widely recognized today. The substituent constants obtained by Hammett's law have σ _p values and σ _m values, which are described in many common books. For example, see the Lange's Handbook of Chemistry by JADean. ) 12th Edition, 1979 (Mc Graw-Hill) or "Chemical Field Supplement", 122, 96-103 pages, 1979 (Nanjiang Hall), "Chemical Reviews" ), 91 volumes, 165 pages to 195 pages, 1991. In the present invention, it is not meant to be limited only to the substituents having the values known from the documents described in the books, even if the value is unknown to the literature, as long as it is included in the measurement according to the Hammett's law. Within the scope, the substituent is of course also included.

Specific examples of the electron withdrawing group having a σ _p value of 0.20 or more and 1.0 or less include an anthracenyl group, a decyloxy group, an amine carbaryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, and a nitro group. Dialkylphosphonium, diarylphosphonium, diarylphosphinyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonium oxide a thiol group, an anthracene group, an sulfonyl group, a thiocyanate group, a thiocarbonyl group, an alkyl group substituted with at least two or more halogen atoms, an alkoxy group substituted with at least two or more halogen atoms, and at least 2 One or more halogen atom-substituted aryloxy groups, an alkylamino group substituted with at least two or more halogen atoms, an alkylthio group substituted with at least two or more halogen atoms, and other pulls having a σ _p value of 0.20 or more An electron-substituted aryl group, a heterocyclic group, a chlorine atom, a bromine atom, an azo group, or a selenocyanate group.

Further, R ³ and R ⁴ may be bonded to each other to form a ring.

Further, it may be in the form of a polymer derived from a monomer in which at least one of R ¹ , R ² , R ³ and R ⁴ is bonded to a vinyl group via a linking group. It may also be a copolymer with other monomers. In the case of a copolymer, as other monomers, there are acrylic acid, α-chloroacrylic acid, and α-alkylacrylic acid (for example, an ester derived from an acrylic acid such as methacrylic acid, preferably a lower alkyl ester and a decylamine, For example, acrylamide, methacrylamide, butyl butyl decylamine, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, acrylic acid 2-ethylhexyl ester, n-hexyl acrylate, octyl methacrylate, and lauryl methacrylate, methylene bis acrylamide, etc., vinyl esters (eg, vinyl acetate, vinyl propionate, and lauric acid) Vinyl esters, etc.), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (such as styrene and its derivatives, such as vinyl toluene, divinylbenzene, vinyl acetophenone, sulfostyrene, and benzene Ethylene sulfinic acid, etc., itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (such as vinyl ether, etc.), maleic acid ester, N-vinyl-2 - pyrrolidone, N-vinylpyridine, 2-vinylpyridine and 4- Alkenyl, pyridine and the like.

Two or more of the above other monomer compounds may also be used in combination. For example, n-butyl acrylate and divinyl benzene, styrene and methyl methacrylate, methyl acrylate and methacrylate may be used in combination.

The ultraviolet ray absorbing agent represented by the general formula (I) can be exemplified by Japanese Patent Publication No. Sho 44-29620, Japanese Patent Laid-Open No. Hei 53-128333, Japanese Patent Laid-Open No. 61-169831, and Japanese Patent Laid-Open No. 63- 53543, Japanese Patent Laid-Open No. Sho 63-53544, Japanese Patent Laid-Open Publication No. SHO63-56651, and the methods described in the WO2009/123109 manual. Specifically, the above-exemplified compound (1) can be synthesized by the method described in paragraph No. 0040 of WO2009/123109.

The curable composition of the present invention may contain an ultraviolet absorber or may not contain an ultraviolet absorber. When the ultraviolet absorber is contained, the content of the ultraviolet absorber is preferably 0.1% by mass to 10% based on the total solid content of the composition. % is more preferably 0.1% by mass to 5% by mass, particularly preferably 0.1% by mass to 3% by mass.

Further, in the present invention, the above various ultraviolet absorbers may be used alone. Two or more types may be used in combination.

In order to remove foreign matter, reduce defects, and the like, it is preferred to filter the curable composition of the present invention with a filter. It is not particularly limited as long as it is a filter used for filtration purposes or the like from the past. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon-6 or nylon-6, 6 or a polyolefin resin such as polyethylene or polypropylene (high density) may be used. A filter containing ultra-high molecular weight or the like. Among these materials, polypropylene (including high density polypropylene) is preferred.

The pore diameter of the filter is suitably from about 0.01 μm to about 7.0 μm, preferably from about 0.02 μm to about 2.5 μm, more preferably from about 0.01 μm to about 1.5 μm. By setting it as the range, it is possible to surely remove fine foreign matter which is mixed into the dissolved pigment or the like and hinders the preparation of the uniform and smooth curable composition in the subsequent step.

Different filters can also be combined when using filters. At this time, the filtration by the first type of filter may be performed only once or twice or more. When two or more filters are combined by using different filters, it is preferred that the pore diameter after the second filtration is larger than the pore diameter of the first filtration. Further, the first type of filters having different pore diameters may be combined in the above range. The aperture here can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, from Japan Pall Co., Ltd., Advantec Toyo Co., Ltd., Japan Nihon Entegris Co., Ltd. (formerly Japan Mico) Choose from various filters provided by Mykrolis Co., Ltd. or Kitz Microfilter Co., Ltd.

As the second filter, a filter formed of the same material as that of the above-described first filter can be used. The pore size of the second filter is suitably from about 0.5 μm to about 7.0 μm, preferably from about 2.5 μm to about 7.0 μm, more preferably from about 4.5 μm to about 6.0 μm. By setting it as the range, it is possible to remove the foreign matter which is mixed into the mixed liquid in a state where the component particles contained in the mixed solution remain, and which hinders the preparation of the uniform and smooth curable composition in the subsequent step.

For example, the filtration by the first type of filter may be carried out only in the dispersion, and after the other components are mixed, the second filtration is performed.

<hardened film>

The cured film of the present invention is a cured film obtained by curing the curable composition.

The cured film of the present invention can be suitably used as an interlayer insulating film. Further, the cured film of the present invention is preferably a cured film obtained by the method for producing a cured film of the present invention to be described later.

According to the curable composition of the present invention, an interlayer insulating film having excellent insulating properties and high transparency at the time of baking at a high temperature can be obtained. The interlayer insulating film which is obtained by using the curable composition of the present invention has high transparency and is excellent in physical properties of the cured film, and thus is useful for use in an organic EL display device or a liquid crystal display device.

The cured film of the present invention can be suitably used as an optical member such as a microlens, an optical waveguide, an antireflection film, a sealing material for a light emitting diode (LED), a wafer coating material for LED, or a touch panel. A cured product for reducing the visibility of the wiring electrode to be used.

In addition, the cured film of the present invention can be suitably used, for example, in a liquid crystal display device, an organic EL device, or the like, a planarization film or an interlayer insulating film, a protective film for a color filter, or a liquid crystal display device. The thickness of the liquid crystal layer in the middle is kept as a fixed spacer, a structural member of a micro electro mechanical system (MEMS) element, or the like.

[Method of Manufacturing Transparent Film (Cured Film)]

The method for producing a transparent film of the present invention includes a step of applying the curable composition onto a wafer by a spray method, a roll coating method, a spin coating method (spin coating method), a bar coating method, or the like; A subsequent first heating step; and, subsequently, a second heating step at a higher temperature.

The conditions in the first heating step are the same as those described in the prebaking conditions in the step (i) in the manufacturing method of the microlens.

The conditions in the second heating step are the same as those described later in the post-baking conditions in the (iv) step in the manufacturing method of the microlens.

<microlens>

Since the curable composition of the present invention can form a transparent film having a high refractive index and a high transmittance, it can be suitably used for, for example, the formation of a microlens and a microlens array.

That is, the curable composition of the present invention is preferably used to form a microlens.

Further, the present invention relates to a microlens formed using a transparent film formed using the curable composition of the present invention.

[Method of Manufacturing Microlens]

The method for producing the microlens using the curable composition of the present invention is not particularly limited, and a method generally used can be applied, and examples thereof include a production method including post-baking treatment of the transparent film described above. The step of shaping further includes a dry etching step.

The step of shaping the transparent film by post-baking treatment is the same as the step detailed as the step (f).

The dry etching step is the same as the step detailed later in the step (g).

A preferred embodiment of the method for producing a microlens using the curable composition of the present invention includes a production method including at least the following steps (i) to (iv).

(i) a step of forming a coating film of the curable composition of the present invention on a substrate.

(ii) a step of irradiating at least a part of the coating film with radiation.

(iii) a step of developing the coating film after the irradiation.

(iv) a step of heating the developed coating film.

Hereinafter, these steps will be described.

(i) steps

In this step, the curable composition is preferably applied to the surface of the substrate as a liquid composition, and then prebaked to remove the solvent to form a coating film on the substrate.

Examples of the substrate include a glass substrate, a tantalum wafer, a substrate on which various metal layers are formed on the surface, and a substrate on which an on-chip color filter for an image sensor is applied.

The coating method is not particularly limited, and for example, a suitable method such as a spray method, a roll coating method, a spin coating method, or a bar coating method can be employed.

The pre-baking conditions vary depending on the type and amount of each component, but are usually from 60 ° C to 120 ° C for about 30 seconds to 15 minutes. The film thickness of the formed coating film is preferably from about 0.5 μm to about 20 μm as a value after prebaking.

(ii) steps

In this step, at least a part of the formed coating film is irradiated with radiation.

When only a part of the coating film is irradiated with radiation, it is irradiated through a mask having a predetermined pattern.

As the radiation to be irradiated, for example, ultraviolet rays such as g-rays and i-rays, far ultraviolet rays such as KrF excimer lasers and ArF excimer lasers, X-rays such as synchrotron radiation, charged particle beams such as electron beams, and the like can be used. Among them, ultraviolet rays are preferred.

Exposure amount corresponding to the configuration and the like of the curable composition is appropriately selected, but is preferably 50J / m ² ~ 2,000J / m ² or so.

(iii) steps

In this step, the exposed coating film is developed with a developing solution, preferably an alkaline developing solution, and the unirradiated portion of the radiation is removed to form a pattern having a predetermined shape.

As the alkaline developing solution, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, and diethylamine can be used. Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, and tetramethyl hydroxide Ammonium, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethyl hydroxide Ammonium, butyltrimethylammonium hydroxide, methyltriammonium hydroxide, dibutyldipentylammonium hydroxide, tetraalkylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzyl A basic aqueous solution of a quaternary ammonium salt such as ammonium hydroxide or triethylbenzylammonium hydroxide or a cyclic amine such as pyrrole or piperidine. These alkaline aqueous solutions may be used singly or in combination of two or more. Further, a water-soluble organic solvent such as methanol or ethanol may be added to the alkaline developing solution, and a surfactant or various organic solvents may be used.

As the developing method, a suitable method such as a puddle developing method, a dipping method, a shaking dipping method, or a shower method can be employed. Further, after development by an alkaline developing solution, washing is usually performed by, for example, running water cleaning.

The development time varies depending on the configuration of the curable composition and the configuration of the developer, but it is usually about 30 seconds to 120 seconds at normal temperature.

(iv) steps

In this step, the developed coating film is heated (post-baking) by a heating means such as a hot plate or an oven to thereby cure the coating film.

In the post-baking, the heating temperature is usually from 120 ° C to 250 ° C, preferably from 160 ° C to 230 ° C. Further, the heating time varies depending on the heating means, and is usually about 5 minutes to 30 minutes when heated on a hot plate, and usually about 30 minutes to 90 minutes when heated in an oven.

Further, in the case of post-baking, a stepwise baking method in which heating is performed twice or more may be employed.

Others as a method of producing a microlens using the curable composition of the present invention A preferred embodiment includes a method of forming at least the following steps (a) to (g).

(a) a step of forming a coating film on a substrate such as a color filter using the curable composition of the present invention; (b) heating the coating film, and then drying (or drying) the coating film Hardening), or a step of obtaining a high refractive index film (transparent film) by exposing at least one of the above-mentioned coating film by a light source (g-ray, i-ray, or the like) of a suitable wavelength; c) a step of forming a resist coating film on the heated high refractive index film; (d) a step of exposing the resist coating film by a light source (g ray, i ray, or the like) of a suitable wavelength; (e) a step of developing the resist coating film after the exposure to form a resist pattern; (f) a step of forming the resist pattern into a lens shape by post-heating; (g) The step of removing the resist pattern and a part of the high refractive index film by dry etching, thereby forming the high refractive index film into a lens shape.

Hereinafter, these steps will be described.

- (a) steps -

In this step, the curable composition of the present invention is applied onto a substrate such as a color filter to form a coating film.

As the coating method, the same method as the above step (i) can be mentioned.

- (b) steps -

In this step, as a preferred embodiment of the heating of the coating film, heat treatment in two stages of prebaking and postbaking is exemplified.

As a condition for prebaking, it is also based on the type or amount of each component, etc. The same, but usually 60 ° C ~ 120 ° C, 30 seconds ~ 15 minutes or so. The film thickness of the formed coating film is preferably from about 0.5 μm to about 20 μm as a value after prebaking. The pre-baking step is sometimes omitted.

Then, heating (post-baking) is performed by a heating means such as a hot plate or an oven, whereby the coating film is cured. The conditions for post-baking are usually from 120 ° C to 300 ° C for about 30 seconds to 60 minutes. Furthermore, hardening can also be promoted by exposure before the post-baking step.

When the coating film is exposed and cured by a light source (g-ray, i-ray, or the like) having an appropriate wavelength, the radiation type to be irradiated is the same as the radiation type and the exposure amount in the above step (ii).

- (c) Step -

In this step, a resist coating film is formed on the high refractive index film. As the resist, a commercially available resist which can be patterned by ultraviolet exposure can be used. The resist coating film is prebaked in the same manner as in the step (a).

- (d) steps -

In this step, the above coating film is exposed to a pattern using a mask. Examples of the radiation to be irradiated include the same radiation type and exposure amount as in the above step (ii).

- (e) steps -

In this step, the exposed resist coating film is developed with a developing solution, preferably an alkaline developing solution, to remove the unirradiated portion or the irradiated portion of the radiation, thereby forming a pattern having a predetermined shape.

As the above alkaline developing solution, the same basicity as the above step (iii) can be mentioned. Developer solution.

As the developing method, the same method as the method described in the above step (iii) can be mentioned.

As the development time, it is the same as the development time described above for the step (iii).

- (f) steps -

In this step, post-heating (post-baking) is performed by a heating means such as a hot plate or an oven, whereby the resist after the pattern formation is deformed into a lens shape. The conditions for post-baking are usually from 120 ° C to 300 ° C for about 30 seconds to 60 minutes. Further, in order to form a lenticular shape, a stepwise baking method in which heating is performed twice or more may be employed.

- (g) steps -

The dry etching can be performed by a known method (for example, Japanese Patent Laid-Open Publication No. 2010-204354).

As the gas for dry etching, for example, the following etching gas is preferably used. CF ₄ , CHF ₃ , SF ₆ , Cl ₂ , C ₂ F ₆ , C ₄ F ₆ , C ₄ F ₈ , C ₅ F ₈ , H ₂ , N ₂ , NH ₃ . One type of gas may be selected from the etching gases, and two or more types of gases may be used in combination. Further, among the etching gases, the fluorine-based gas is preferably selected from the group consisting of CF ₄ , C ₄ F ₆ , C ₂ F ₆ , C ₄ F ₈ , and CHF from the viewpoint of maintaining the squareness of the portion to be etched. At least one or more of the group of ₃ is more preferably CF ₄ or C ₄ F ₆ , and most preferably a mixed gas of CF ₄ and C ₄ F ₆ .

Further, from the viewpoint of maintaining the partial pressure control stability of the etching plasma and the perpendicularity of the shape to be etched, the mixed gas used in the dry etching preferably contains other gases in addition to the fluorine-based gas and oxygen. . The other gas preferably contains a rare gas selected from the group consisting of helium (He), neon (Ne), argon (Ar), helium (Kr), and xenon (Xe), and contains a chlorine atom, a fluorine atom, and a bromine. a halogen-based gas (for example, CCl ₄ , CClF ₃ , AlF ₃ , AlCl ₃ or the like) having a halogen atom such as an atom, at least one selected from the group consisting of N ₂ , CO, and CO ₂ , more preferably containing a selected from He and Ar. At least one of the group of Kr, N ₂ , and Xe is more preferably at least one selected from the group consisting of He, Ar, and Xe.

Further, when the partial pressure control stability of the etching plasma and the perpendicularity of the shape to be etched can be maintained, the mixed gas used in the dry etching may contain only fluorine-based gas and oxygen.

In this way, the target microlens can be manufactured.

According to the method for producing a microlens of the present invention, it is possible to easily form a high-definition microlens and microlens array having excellent characteristics (for example, high refractive index and high permeability) with high product yield.

<Undercoat film of color filter>

Further, the curable composition of the present invention can also be used as an undercoat film of a color filter. Since the curable composition of the present invention can form a transparent and flat coating film, it can be suitably used as a primer film.

That is, the curable composition for the undercoat film of the color filter of the curable composition of the present invention is also preferable.

The undercoat film is preferably an undercoat film of a color filter formed by the following steps.

(i') using the curable composition of the present invention on the substrate on which the element is formed a step of coating a film; (ii') heating the coating film, followed by drying (or drying and hardening) of the coating film, thereby obtaining a transparent film; (iii') by a known method And forming a color filter on the transparent film.

The formation of the coating film and the transparent film can be carried out in accordance with the method described in the above [Microlens].

The undercoat film of the microlens and the color filter of the present invention is an undercoat film formed of the curable composition of the present invention, has an excellent balance of characteristics, and can be extremely suitably used for various office automation (Office Automation, OA) Liquid crystal display elements such as machines, liquid crystal televisions, mobile phones, projectors, etc., imaging optical systems for crystal-loaded color filters such as facsimile machines, electronic photocopiers, solid-state imaging devices, optical fiber connectors, and the like.

<Solid photographic element>

The solid-state imaging device of the present invention is characterized by comprising a microlens formed using the curable composition of the present invention described above.

Since the solid-state imaging device of the present invention has a microlens having a high refractive index and high permeability, noise can be reduced, and excellent color reproducibility can be exhibited.

The solid-state imaging device of the present invention is configured to include a microlens formed using the curable composition of the present invention, and is not particularly limited as long as it functions as a solid-state imaging device, and examples thereof include a composition on a substrate. a plurality of photodiodes of a light receiving region of a solid-state imaging device (Charge Coupled Device (CCD) image sensor, a complementary metal oxide semiconductor (CMOS) image sensor, etc.) crystal The light-receiving element such as 矽 has a configuration in which the undercoat film is provided under a color filter, and the configuration of the above-described microlens is provided on the color filter.

The method for producing a solid-state imaging device of the present invention is not particularly limited, and one of the preferred embodiments includes the steps of forming a red color on a substrate for a solid-state imaging device having at least a photodiode, a light-shielding film, and a device protective film. a step of a pixel, a blue pixel, and a green pixel; a step of applying the hardenable composition and heating; a step of forming a resist pattern; performing a post-baking treatment to form the formed resist pattern a step of forming a lenticular shape; and a dry etching step.

a step of applying a curable composition and heating, a step of forming a coating film on the substrate in the steps (a) and (b) of the method for producing the microlens, and performing a coating film on the coating film The steps of drying (or drying and hardening) of the coating film after heating are the same.

The step of forming the resist pattern is the same as the steps (d) and (e) in the method of manufacturing the above microlens.

The step of forming the formed resist pattern into a lenticular shape as the post-baking treatment is the same as the step (f) in the above-described method of manufacturing the microlens.

The dry etching step is the same as the step (g) in the above-described method of manufacturing a microlens.

<Liquid crystal display device>

A liquid crystal display device of the present invention is characterized by comprising the cured film of the present invention described above.

The liquid crystal display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the curable composition of the present invention, and a known liquid crystal display device having various structures can be cited.

Specific examples of the thin film transistor (TFT) included in the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

Further, examples of the liquid crystal driving method which can be employed in the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and a coplanar switching (In-Plane Switching, IPS). ), Fringe Field Switching (FFS) method, Optical Compensated Bend (OCB) method, etc.

In the panel structure, the cured film of the present invention can be used in a liquid crystal display device of a color filter on Array (COA) type, and can be used, for example, in Japanese Laid-Open Patent Publication No. 2005-284291. The organic insulating film (212) described in Japanese Laid-Open Patent Publication No. 2005-346054, or the organic insulating film (212).

In addition, as a specific alignment method of the liquid crystal alignment film which can be used for the liquid crystal display device of the present invention, a rubbing alignment method, a photoalignment method, and the like can be given. In addition, Japanese Patent Laid-Open Publication No. 2003-149647 or Japanese Patent Laid-Open No. 2011-257734 The Polymer Disstained Alignment (PSA) technique described in the publication of the Japanese Patent Publication No.

FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is provided with elements of the TFT 16 corresponding to all the pixels disposed between the two glass substrates 14 and the glass substrate 15 to which the polarizing film is attached. . Among the elements formed on the glass substrate, an ITO transparent electrode 19 on which a pixel electrode is formed is wired by a contact hole 18 formed in the cured film 17. A layer of the liquid crystal 20 and an RGB color filter 22 in which a black matrix is disposed are provided on the ITO transparent electrode 19.

The light source as the backlight is not particularly limited, and a known light source can be used. For example, white LED, blue. red. Multicolor LEDs such as green, fluorescent lamps (cold cathode tubes), organic EL, etc.

Further, the liquid crystal display device can also be a 3D (stereoscopic) type device or a touch panel type device. Further, it can be set to a flexible type, and can be used as the second interlayer insulating film (48) described in Japanese Laid-Open Patent Publication No. 2011-145686, or as described in Japanese Laid-Open Patent Publication No. 2009-258758. Interlayer insulating film (520).

<Organic EL display device>

The organic EL display device of the present invention is characterized by comprising the cured film of the present invention described above.

The organic EL display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the curable composition of the present invention. Various known organic EL display devices or liquid crystal display devices having various structures are listed.

Specific examples of the TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous germanium-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

FIG. 2 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and having a planarization film 4.

A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. After the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. The wiring 2 is a wire for connecting the organic EL element formed between the TFTs 1 or in the subsequent step and the TFT 1.

Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried.

A bottom emission type organic EL element is formed on the planarization film 4. That is, the first electrode 5 including ITO is connected to the wiring 2 via the contact hole 7 to be formed on the planarization film 4. Further, the first electrode 5 corresponds to the anode of the organic EL element.

The insulating film 8 having a shape covering the periphery of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Furthermore, although not shown in FIG. 2, it is sequentially arranged through a desired pattern mask. Performing vapor deposition to form a hole transport layer, an organic light-emitting layer, and an electron transport layer, and then forming a second electrode containing Al on the entire upper surface of the substrate, and then using a sealing glass plate and an ultraviolet curing epoxy resin An active matrix type organic EL display device in which a TFT 1 for driving the organic EL element is connected to each other is obtained by bonding and sealing.

Since the curable composition of the present invention is excellent in curability and cured film properties, a resist pattern formed using the curable composition of the present invention is used as a partition wall as a structural member of a MEMS element or as a mechanically driven part. Part of it is assembled and used. Examples of such a MEMS element include a surface acoustic wave filter, a bulk acoustic wave filter, a gyro sensor, a micro shutter for display, an image sensor, and an electronic device. Paper, inkjet head, biochip, sealant and other parts. More specific examples are exemplified in Japanese Patent Laid-Open Publication No. 2007-522531, Japanese Patent Laid-Open Publication No. 2008-250200, and Japanese Patent Laid-Open No. 2009-263544.

The curable composition of the present invention is excellent in flatness and transparency, and can be used for forming a bank layer (16) and a planarizing film (see) in Fig. 2 of JP-A-2011-107476. 57) The partition wall (12) and the flattening film (102) described in Fig. 4 (a) of Japanese Patent Laid-Open Publication No. 2010-9793, and the description of Fig. 10 of Japanese Patent Laid-Open Publication No. 2010-27591 The deposition layer (221) and the third interlayer insulating film (216b), the second interlayer insulating film (125) and the third interlayer insulating film described in FIG. 4(a) of JP-A-2009-128577 ( 126) The flattening film (12) and the pixel separation insulating film (14) described in Fig. 3 of Japanese Laid-Open Patent Publication No. 2010-182638.

<Touch Panel Display Device>

A touch panel display device of the present invention includes a capacitance type input device having a cured film of the present invention. Further, the capacitance type input device of the present invention is characterized by having the cured film of the present invention.

The capacitive input device of the present invention preferably has a front panel and has at least the following elements (1) to (5) on the non-contact side of the front panel, and the above (4) is the hardening of the present invention. Things.

(1) mask layer

(2) a plurality of first transparent electrode patterns formed by the plurality of pad portions extending in the first direction via the connection portion

(3) a plurality of second transparent electrode patterns electrically insulated from the first transparent electrode pattern and including a plurality of pad portions formed to extend in a direction crossing the first direction

(4) an insulating layer electrically insulating the first transparent electrode pattern from the second transparent electrode pattern

(5) a conductive element electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern and different from the first transparent electrode pattern and the second transparent electrode pattern

In the capacitance type input device of the present invention, it is preferable to further provide a transparent protective layer so as to cover all or a part of the elements (1) to (5), and more preferably The above transparent protective layer is a cured film of the present invention.

First, the configuration of the capacitance type input device will be described. 3 is a cross-sectional view showing the configuration of a capacitance type input device. In FIG. 3, the capacitive input device 30 includes a front panel 31, a mask layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, a conductive element 36, and a transparent protective layer 37. .

The front panel 31 is made of a light-transmissive substrate such as a glass substrate, and tempered glass such as Gorilla Glass of Corning Co., Ltd. can be used. In addition, in FIG. 3, the side of the front panel 31 in which each element is provided is called a non-contact surface. In the capacitance type input device 30 of the present invention, a finger or the like is brought into contact with a contact surface (opposite surface of the non-contact surface) of the front panel 31, and the like. Hereinafter, the front panel may be referred to as a "substrate".

Further, a mask layer 32 is provided on the non-contact surface of the front panel 31. The mask layer 32 is a frame-like pattern formed around the display area on the non-contact side of the front panel of the touch panel, and is formed in order to prevent the lead wires or the like from being seen.

In the capacitance type input device of the present invention, as shown in FIG. 4, the mask layer 32 is provided so as to cover a portion of the front panel 31 (a region other than the input surface in FIG. 4). Further, in the front panel 31, as shown in FIG. 4, the opening 38 may be provided in a part. In the opening 38, a mechanical switch that uses pressing can be provided.

As shown in FIG. 5, a plurality of first transparent electrode patterns 33, a plurality of second transparent electrode patterns 34, and an insulating layer 35 are formed on the contact surface of the front panel 31, and the plurality of first transparent electrode patterns 33 are The pad portion is formed to extend in the first direction via the connecting portion, the plurality of second transparent electrode patterns 34 being electrically insulated from the first transparent electrode pattern 33 and extending in a direction crossing the first direction In the plurality of pad portions formed, the insulating layer 35 electrically insulates the first transparent electrode pattern 33 from the second transparent electrode pattern 34. The first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 to be described later may be, for example, indium tin oxide (ITO) or indium zinc oxide (Indium Zinc Oxide, IZO). It is made of a light conductive metal oxide film. Examples of such a metal film include an ITO film; a metal film of Al, Zn, Cu, Fe, Ni, Cr, Mo, or the like; a metal oxide film of SiO ₂ or the like. In this case, the film thickness of each element can be set to 10 nm to 200 nm. Further, since the amorphous ITO film is formed into a polycrystalline ITO film by firing, the electric resistance can be reduced. Further, the first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 to be described later may be produced using a photocurable transfer material having the above-described conductive fiber. A hardening composition. Further, when the first conductive pattern or the like is formed by ITO or the like, reference is made to paragraphs [0014] to [0016] of Japanese Patent No. 4,506,785.

Further, at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 may extend across the non-contact surface of the front panel 31 and the surface of the mask layer 32 opposite to the front panel 31. Settings. FIG. 3 shows a view in which the second transparent electrode pattern is provided across the non-contact surface of the front panel 31 and the surface of the mask layer 32 opposite to the front panel 31.

The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. 5. Figure 5 is a view showing the first transparent electrode pattern and the second through in the present invention An explanatory diagram of an example of a bright electrode pattern. As shown in FIG. 5, the first transparent electrode pattern 33 is formed by the pad portion 33a extending in the first direction via the connection portion 33b. In addition, the second transparent electrode pattern 34 is electrically insulated from the first transparent electrode pattern 33 by the insulating layer 35, and is formed by extending in a direction crossing the first direction (the second direction in FIG. 5). Pad part. Here, when the first transparent electrode pattern 33 is formed, the pad portion 33a and the connection portion 33b may be integrally formed, or only the connection portion 33b may be formed, and the pad portion 33a and the second transparent electrode pattern 34 may be integrated. To make (patterned). When the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 5, each layer is formed in such a manner that a part of the connection portion 33b is connected to a part of the pad portion 33a, and The transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by the insulating layer 35.

In FIG. 3, the conductive element 36 is provided on the surface side of the mask layer 32 opposite to the front panel 31. The conductive element 36 is an element that is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 and that is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34 . FIG. 3 shows a diagram in which the conductive element 36 is connected to the second transparent electrode pattern 34.

In addition, in FIG. 3, the transparent protective layer 37 is provided so that all the components may be covered. The transparent protective layer 37 can be configured to cover only a part of each constituent element. The insulating layer 35 and the transparent protective layer 37 may be the same material or different materials.

<Electrostatic capacitance type input device and electrostatic capacitance type input device Touch panel display device >

The capacitive touch input device obtained by the manufacturing method of the present invention and the touch panel display device including the capacitive input device as constituent elements can apply "the latest touch panel technology" (release technology of July 6, 2009) Techno Times (shares), Editor-in-Chief of Sangu Yuji, "Technology and Development of Touch Panels", CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Materials, Competition The composition disclosed in Cypress Semiconductor Corporation Application Note AN2292, and the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. In addition, "parts" and "%" are quality standards unless otherwise specified.

Further, in the examples, the acid value was determined by a potential difference method (solvent was tetrahydrofuran/water = 54/6 (volume ratio), and the titration solution was 0.1 N aqueous sodium hydroxide solution (acid value)).

In addition, the following weight average molecular weight was measured by: HPC-8220GPC (manufactured by Tosoh), guard column: TSKguardcolumn SuperHZ-L, column: TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperHZ3000 The TSKgel SuperHZ2000 was directly connected, and 10 μl of a tetrahydrofuran solution having a sample concentration of 0.1% by mass was injected at a column temperature of 40 ° C, and tetrahydrofuran as a dissolution solvent was flowed at a flow rate of 0.35 ml per minute, and a refractive index (Refractive Index, RI) was used. The detecting device detects the peak value of the sample. The calculation was performed using a calibration curve made using standard polystyrene.

(Synthesis Example 1) Synthesis of Polymer Compound (C-5)

The polymer compound (C- is synthesized according to the synthesis method described in paragraph 0266 to paragraph 0348 of the corresponding Japanese Patent Application Laid-Open No. 2010/233595). 5). Specifically, it is as follows.

400 parts of dipentaerythritol hexa(3-decyl propionate) [(33); manufactured by 堺Chemical Industries, Ltd.], and compound (A-3) 232.6 having the following adsorption sites and having a carbon-carbon double bond The fraction was dissolved in 1476.1 parts of 1-methoxy-2-propanol and then heated to 90 ° C under a stream of nitrogen. The addition ratio at this time was 1.0:3.5 in terms of molar ratio.

To this was added 2.06 parts of dimethyl 2,2'-azobis(2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 2 hours. Further, 2.06 parts of V-601 was added, followed by a reaction at 90 ° C for 2 hours under a nitrogen stream. A 30% by mass solution of a thiol compound (B-5) obtained by adding a compound (A-3) to a part of the sulfur atom of the compound (33) by cooling to room temperature (25 ° C) .

a mixed solution of 652.81 parts of a 30% by mass solution of the above thiol compound (B-5) and 554.16 parts of methyl methacrylate (M-1) under a nitrogen gas stream Heat to 90 °C. The dimethyl 2,2'-azobis(2-methyl propionate) [V-601, manufactured by Wako Pure Chemical Industries Co., Ltd.] 3.823 parts was dissolved in propylene glycol monomethyl ether B over 2 hours. A solution of 402.52 parts of the acid ester was then heated at 90 ° C for 2 hours. Further, 1.274 parts of V-601 was added, and then reacted at 90 ° C for 2 hours under a nitrogen stream, and 1.274 parts of V-601 was further added, followed by a reaction at 90 ° C for 2 hours under a nitrogen stream. Thereafter, 890.51 parts of propylene glycol monomethyl ether acetate was added, and the mixture was cooled to room temperature to obtain a polymer compound shown below (C-5: polystyrene-equivalent weight average molecular weight was 6,400, and the acid value was A 30% by mass solution of 80 mg KOH/g).

(Synthesis Example 2) Synthesis of Polymer Compound (C-27)

The polymer compound (C- is synthesized according to the synthesis method described in paragraph 0266 to paragraph 0348 of the corresponding Japanese Patent Application Laid-Open No. 2010/233595). 27). Specifically, it is as follows.

65.0 parts of dipentaerythritol hexa(3-decyl propionate) [(33); manufactured by 堺Chemical Industries, Ltd.], and a compound (A-16) having a carbon-carbon double bond having the following adsorption sites and 44.5 And 27.0 parts of the compound (A-3) are dissolved in 1-methoxy-2-propanol In 318.4 parts, it was then heated to 90 ° C under a stream of nitrogen. The addition ratio of (33) to (A-16) and (A-3) at this time was 1.0:2.5:2.5 in terms of a molar ratio.

To this was added 0.478 parts of dimethyl 2,2'-azobis(2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 2 hours. Further, 0.478 parts of V-601 was added, followed by a reaction at 90 ° C for 2 hours under a nitrogen stream. 30 of the thiol compound (B-27) obtained by adding the compound (A-3) and the compound (A-16) to a part of the sulfur atom of the compound (33) by cooling to room temperature Mass % solution.

Under a nitrogen gas stream, a mixed solution of 150.3 parts of a 30% by mass solution of the above thiol compound (B-27) and 54.9 parts of methyl methacrylate (M-1) was heated to 90 °C. The dimethyl 2,2'-azobis(2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries Co., Ltd.] 0.379 parts was dissolved in propylene glycol 1-single over a period of 2 hours. A solution of 39.9 parts of ether 2-acetate was then heated at 90 ° C for 2 hours. Further, 0.126 parts of V-601 was added, and then reacted at 90 ° C for 2 hours under a nitrogen stream, 0.126 parts of V-601 was further added, and then reacted at 90 ° C for 2 hours under a nitrogen stream. Thereafter, 88.3 parts of propylene glycol 1-monomethyl ether 2-acetate was added, and the mixture was cooled to room temperature, whereby the polymer compound shown below (C-27: polyphenylene) was obtained. A 30 mass% solution having a weight average molecular weight of 4,400 and an acid value of 77 mgKOH/g in terms of ethylene.

(Synthesis Example 3) Synthesis of Polymer Compound (C-28)

The polymer compound (C- is synthesized according to the synthesis method described in paragraph 0266 to paragraph 0348 of the corresponding Japanese Patent Application Laid-Open No. 2010/233595). 28). Specifically, it is as follows.

65.0 parts of dipentaerythritol hexa(3-decyl propionate) [(33); 堺Chemical Industries, Ltd.], and a compound (A-17) 44.5 having the following adsorption sites and having a carbon-carbon double bond A solution of 27.0 parts of the compound (A-3) was dissolved in 318.4 parts of 1-methoxy-2-propanol, and then heated to 90 ° C under a nitrogen gas stream. The addition ratio of (33) to (A-17) and (A-3) at this time was 1.0:2.5:2.5 in terms of a molar ratio.

To this was added 0.478 parts of dimethyl 2,2'-azobis(2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 2 hours. Further, 0.478 parts of V-601 was added, followed by a reaction at 90 ° C for 2 hours under a nitrogen stream. Adding a compound to a part of the sulfur atom of the compound (33) by cooling to room temperature A 30% by mass solution of the thiol compound (B-28) (A-3) and the compound (A-17).

Under a nitrogen gas stream, a mixed solution of 150.3 parts of a 30% by mass solution of the above thiol compound (B-28) and 54.9 parts of methyl methacrylate (M-1) was heated to 90 °C. The dimethyl 2,2'-azobis(2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries Co., Ltd.] 0.379 parts was dissolved in propylene glycol 1-single over a period of 2 hours. A solution of 39.9 parts of ether 2-acetate was then heated at 90 ° C for 2 hours. Further, 0.126 parts of V-601 was added, and then reacted at 90 ° C for 2 hours under a nitrogen stream, 0.126 parts of V-601 was further added, and then reacted at 90 ° C for 2 hours under a nitrogen stream. Thereafter, 88.3 parts of propylene glycol 1-monomethyl ether 2-acetate was added, and the mixture was cooled to room temperature to obtain a polymer compound shown below (C-28: polystyrene-equivalent weight average molecular weight was 4,300 A 30% by mass solution having an acid value of 77 mgKOH/g.

(Synthesis Example 4) Synthesis of Polymer Compound (C-43)

The polymer compound (C- is synthesized according to the synthesis method described in paragraph 0266 to paragraph 0348 of the corresponding Japanese Patent Application Laid-Open No. 2010/233595). 43). Specifically, it is as follows.

70.0 parts of dipentaerythritol hexa(3-decyl propionate) [(33); manufactured by 堺Chemical Industries, Ltd.], and compound (A-23) having the following adsorption sites and having a carbon-carbon double bond 17.7 46.5 parts of the compound (A-3) was dissolved in 313.2 parts of 1-methoxy-2-propanol, and then heated to 90 ° C under a nitrogen gas stream. The addition ratio of (33) to (A-23) and (A-3) at this time was 1.0:1.0:4.0 in terms of a molar ratio.

To this was added 0.515 parts of dimethyl 2,2'-azobis(2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 2 hours. Further, 0.515 parts of V-601 was added, followed by a reaction at 90 ° C for 2 hours under a nitrogen stream. 30 of the thiol compound (B-43) obtained by adding the compound (A-3) and the compound (A-23) to a part of the sulfur atom of the compound (33) by cooling to room temperature Mass % solution.

Under a nitrogen gas stream, a mixed solution of 155.6 parts of a 30% by mass solution of the above thiol compound (B-43) and 93.3 parts of methyl methacrylate (M-1) was heated to 90 °C. Diluted with dimethyl 2,2'-azobis(2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries Co., Ltd.] 0.644 parts was dissolved in propylene glycol 1-single for 2 hours. A solution of 67.8 parts of ether 2-acetate was then heated at 90 ° C for 2 hours. Further, 0.215 parts of V-601 was added, and then reacted at 90 ° C for 2 hours under a nitrogen gas stream, 0.215 parts of V-601 was further added, and then reacted at 90 ° C for 2 hours under a nitrogen gas stream. Thereafter, 150.0 parts of propylene glycol 1-monomethyl ether 2-acetate was added, and the mixture was cooled to room temperature to obtain a polymer compound shown below (C-43: weight average molecular weight in terms of polystyrene was 6,400) A 30% by mass solution having an acid value of 99 mgKOH/g.

(Synthesis Example 5) Synthesis of Polymer Compound (C-46)

The polymer compound (C- is synthesized according to the synthesis method described in paragraph 0266 to paragraph 0348 of the corresponding Japanese Patent Application Laid-Open No. 2010/233595). 46). Specifically, it is as follows.

31.0 parts of dipentaerythritol hexa(3-decyl propionate) [(33); 堺Chemical Industries, Ltd.], and a compound (A-26) 8.88 having the following adsorption sites and having a carbon-carbon double bond A solution of 20.6 parts of the compound (A-3) was dissolved in 141.1 parts of 1-methoxy-2-propanol, and then heated to 90 ° C under a nitrogen gas stream. The addition ratio of (33) to (A-26) and (A-3) at this time was 1.0:1.0:4.0 in terms of a molar ratio.

To this was added 0.228 parts of dimethyl 2,2'-azobis(2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 2 hours. Further, 0.228 parts of V-601 was added, followed by a reaction at 90 ° C for 2 hours under a nitrogen gas stream. 30 of the thiol compound (B-46) obtained by adding the compound (A-3) and the compound (A-26) to a part of the sulfur atom of the compound (33) by cooling to room temperature Mass % solution.

Heating a mixed solution of a 30% by mass solution of the above thiol compound (B-46), 157.4 parts, and a methyl methacrylate (M-1), 92.8 parts, under a nitrogen gas stream. To 90 ° C. Diluted with dimethyl 2,2'-azobis(2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries Co., Ltd.] 0.640 parts was dissolved in propylene glycol 1-monomethyl for 2 hours. A solution of 67.40 parts of ether 2-acetate was then heated at 90 ° C for 2 hours. Further, 0.213 parts of V-601 was added, and then reacted at 90 ° C for 2 hours under a nitrogen stream, 0.213 parts of V-601 was further added, and then reacted at 90 ° C for 2 hours under a nitrogen stream. Thereafter, 149.1 parts of propylene glycol 1-monomethyl ether 2-acetate was added, and the mixture was cooled to room temperature to obtain a polymer compound shown below (C-46: polystyrene-equivalent weight average molecular weight was 6,600) A 30% by mass solution having an acid value of 99 mgKOH/g.

(Synthesis Example 6) Synthesis of Polymer Compound (C-48)

The polymer compound (C- is synthesized according to the synthesis method described in paragraph 0266 to paragraph 0348 of the corresponding Japanese Patent Application Laid-Open No. 2010/233595). 48). Specifically, it is as follows.

70.0 parts of dipentaerythritol hexa(3-decyl propionate) [(33); 堺Chemical Industries, Ltd.], and compound (A-28) 11.6 having the following adsorption sites and having a carbon-carbon double bond And 46.5 parts of the compound (A-3) are dissolved in 1-methoxy-2-propanol In 299.0 parts, it was then heated to 90 ° C under a stream of nitrogen. The addition ratio of (33) to (A-28) and (A-3) at this time was 1.0:1.0:4.0 in terms of a molar ratio.

To this was added 0.515 parts of dimethyl 2,2'-azobis(2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 2 hours. Further, 0.515 parts of V-601 was added, followed by a reaction at 90 ° C for 2 hours under a nitrogen stream. 30 of the thiol compound (B-48) obtained by adding the compound (A-3) and the compound (A-28) to a part of the sulfur atom of the compound (33) by cooling to room temperature Mass % solution.

Under a nitrogen gas stream, a mixed solution of 150.8 parts of a 30% by mass solution of the above thiol compound (B-48) and 94.8 parts of methyl methacrylate (M-1) was heated to 90 °C. The dimethyl 2,2'-azobis(2-methylpropionate) [V-601, manufactured by Wako Pure Chemical Industries Co., Ltd.] 0.654 parts was dissolved in propylene glycol 1-monomethylate dropwise over 2 hours. A solution of 68.8 parts of ether 2-acetate was then heated at 90 ° C for 2 hours. Further, 0.218 parts of V-601 was added, and then reacted at 90 ° C for 2 hours under a nitrogen gas stream, 0.218 parts of V-601 was further added, and then reacted at 90 ° C for 2 hours under a nitrogen gas stream. Thereafter, 152.3 parts of propylene glycol 1-monomethyl ether 2-acetate was added, and After cooling to room temperature, a 30 mass% solution of the polymer compound (C-48: polystyrene-equivalent weight average molecular weight: 6400, acid value: 99 mgKOH/g) shown below was obtained.

Polymer compound (C-1) to (C-4), polymer compound (C-6) to polymer compound (C-26), polymer compound (C-29) to polymer compound (C-42) ), polymer compound (C-44), polymer compound (C-45), polymer compound (C-47), polymer compound (C-49) ~ polymer compound (C-61), also based on Japan The synthesis method described in the paragraphs 0266 to 0348 of the corresponding Japanese Patent Application Laid-Open No. 2010/233595 (paragraph 0289 to paragraph 0429) is synthesized. Specifically, the type of "a compound having a (m+n)-valent linking group R ¹ and a mercapto group" (corresponding to the above-mentioned "compound having 3 to 10 mercapto groups in one molecule") and Addition amount, "compound having a substituent A ¹ and a carbon-carbon double bond" (corresponding to the type and amount of "the compound having an adsorption site and having a carbon-carbon double bond"), and "formation of P ¹ or P" ^The polymer compound (C-1) to (C-) was synthesized in the same manner as in the above Synthesis Example 1 to Synthesis Example 6 except for the type and amount of the monomer (the "vinyl monomer"). 4), polymer compound (C-6) ~ polymer compound (C-26), polymer compound (C-29) ~ polymer compound (C-42), polymer compound (C-44), polymer Compound (C-45), polymer compound (C-47), polymer compound (C-49) to polymer compound (C-61).

The polymer compound (C-1) to the polymer compound (C-61) synthesized as a raw material, and a "compound having a (m+n)-valent linking group R ¹ and a mercapto group, which are raw materials, are used as raw materials. "Compound having a substituent A ¹ and a carbon-carbon double bond" (inclusive, each of which is a molar ratio of the molar ratio), and a "P ¹ or P ² -forming monomer" which is a raw material (in combination, the respective addition amounts are indicated). Mohr ratio), m, n in the formula (1) or the formula (2), P ¹ in the formula (1) or the number of repeats k of the repeating unit in P ² in the formula (2), The acid value and the weight average molecular weight are summarized in Table 1 below.

In the above Table 1, the number of m and the number of n represent m and n in the formula (1) or the formula (2). For example, when the compound (A-8) is used in combination with the compound (A-3) as in (C-18) (the molar ratio is 1:4), the number 3 as the n number is derived from the compound (A). The structure of -8) is combined with the structure derived from the compound (A-3).

The k number represents the number of repetitions k of the repeating unit in P ¹ in the general formula (1) or P ² in the general formula (2). For example, when the monomer (M-1) is mixed with the monomer (M-2) as in (C-32) (the molar amount of the molar ratio is 1:1), 13 as the k number is derived from the single The total number of repetitions of the repeating unit of the body (M-1) and the repeating unit derived from the monomer (M-2).

As the "compound having a (m + n) valent linking group R ¹ and a thiol group in the above Table 1 (corresponding to the above "a compound having 3 to 10 fluorenyl groups in one molecule"), the following compound (18) was used. ), Compound (27), Compound (33).

As the "compound having a substituent A ¹ and a carbon-carbon double bond" in the above Table 1 (corresponding to the above "a compound having an adsorption site and having a carbon-carbon double bond"), the following compound (A-1) was used. ~ Compound (A-32).

As the "monomer forming P ¹ or P ² " (corresponding to the above "vinyl monomer") in the above Table 1, the above monomer (M-1) to monomer (M-9), monomer ( M-14) ~ monomer (M-16) is suitable for use.

Hereinafter, the structure of the polymer compound (C-1) to polymer compound (C-61) to be synthesized will be described.

(Synthesis Example 7) Synthesis of Macromonomer A5

Under a nitrogen atmosphere, 35.0 parts of 2-ethylhexanol, 215.0 parts of ε-caprolactone and 0.20 parts of dibutyltin laurate were heated at 90 ° C for 5 hours, followed by heating at 110 ° C for 1 hour to obtain a polyester. Single hydroxyl body. The end of the reaction was confirmed by measuring the disappearance of ε-caprolactone by nuclear magnetic resonance (NMR). Then, after being placed under air, 0.071 parts of 2,6-di-t-butyl-4-methylphenol (BHT) and 37.7 parts of allyl succinic anhydride were added, and the mixture was reacted at 110 ° C for 8 hours to obtain Macromonomer A5 shown below. The end of the reaction was confirmed by measuring the disappearance of allyl succinic anhydride by 95% or more by NMR. The macromonomer A5 had a polystyrene-equivalent weight average molecular weight of 1,400 and an acid value of 54 mgKOH/g.

(Synthesis Example 8) Synthesis of macromonomer E5

200 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and then heated to 80 ° C while injecting nitrogen gas into the vessel. 40.1 parts of thioethanol, 360 parts of methyl methacrylate, 200 parts of propylene glycol monomethyl ether acetate, and 35.5 parts of V-601 were added to other containers and stirred, and then heated to 80 ° C for 2 hours. Stir in the reaction vessel. Further, after reacting at the same temperature for 2 hours, 35.5 parts of V-601 was added, and the reaction was further continued at 90 ° C for 1 hour, whereby a polymethyl methacrylate monohydroxy group was obtained. The end of the reaction was confirmed by measuring the disappearance of the double bond portion of methyl methacrylate by 99% or more by NMR. Then, after being placed under air, 0.134 g of 2,6-di-t-butyl-4-methylphenol and 71.2 g of allyl succinic anhydride were added, and the mixture was reacted at 110 ° C for 8 hours, whereby the following was obtained. Macromonomer E5 (solid content concentration = 28.9% by mass). The end of the reaction was confirmed by measuring the disappearance of allyl succinic anhydride by 95% or more by NMR. The macromonomer E5 had a polystyrene-equivalent weight average molecular weight of 1,600 and an acid value of 64 mgKOH/g.

Synthesis of macromonomer A1 to macromolecule in the same manner as in Synthesis Example 7. Monomer A1 to macromonomer E4 were synthesized in the same manner as in Synthesis Example 8 as monomer A4. The structural formula and physical property values of the respective macromonomers are shown below.

(Synthesis Example 9) Synthesis of polymer compound (C-102)

To the reaction vessel, 20 parts of dipentaerythritol hexa(3-decyl propionate) [(33); manufactured by 堺Chemical Industry Co., Ltd.], 81.9 parts of macromonomer A5, the above-mentioned adsorption site and having carbon-carbon double were added. Key compound (A-1) 7.67 parts, propylene glycol monomethyl ether B The ester was 255 parts and then heated to 90 ° C while injecting nitrogen into the vessel. After stirring at the same temperature for 15 minutes, 0.71 part of V-601 was added to start the reaction. After reacting at the same temperature for 2 hours, 0.71 part of V-601 was added, and the reaction was further continued at 90 ° C for 2 hours, whereby the polymer compound shown below (C-102: polystyrene-equivalent weight average molecular weight) was obtained. It is a 30 mass% solution of 4600 and an acid value of 108 mgKOH/g). The end of the reaction was confirmed by measuring the disappearance of the double bond sites of the macromonomer A5 and pentenoic acid by 95% or more by NMR.

The type and amount of "a compound having a (m+n)-valent linking group R ¹ and a mercapto group" (corresponding to the above-mentioned "a compound having 3 to 10 mercapto groups in one molecule") "Compounds having a substituent A ¹ and a carbon-carbon double bond" (corresponding to the above-mentioned "compound having a carbon-carbon double bond with an adsorption site"), the amount of addition, and "macromonomer" (corresponding to In addition to the type and amount of the compound of the polymer chain represented by P ¹ , P ² or P ³ , the polymer compound is synthesized in the same manner as in the synthesis of the above-mentioned Synthesis Example 9 [polymer compound (C-102)]. (C-101), polymer compound (C-103) ~ polymer compound (C-119). The macromonomer used in the synthesis of the polymer compound (C-110) to the polymer compound (C-119) is appropriately selected from the following structures and used.

The polymer compound (C-101) to polymer compound (C-119) synthesized as a raw material, "a compound having a (m + n) valent linking group R ¹ and a fluorenyl group", which is a raw material, is used as a raw material. "Compound having a substituent A ¹ and a carbon-carbon double bond" (indicating the molar ratio of each of them), a "macromonomer" as a raw material, an acid value, and a weight average molecular weight are summarized in Table 3 below. in.

Hereinafter, the structure of the polymer compound (C-101) to polymer compound (C-119) synthesized will be described.

<Example 1>

[Preparation of titanium dioxide dispersion (dispersion composition)]

Ultra Apex Mill manufactured by Kotobuki Industries Co., Ltd. was used as a circulation type dispersing device (bead mill), and the following composition was as follows The mixture was subjected to dispersion treatment to obtain a dispersion of titanium dioxide as a dispersion composition.

~Comment~

. Titanium dioxide (TTO-51 (C) manufactured by Ishihara Industry Co., Ltd.) (purity of 75% or more): 181.8 parts

. Dispersing agent (polymer compound (B)) C-4 (30% by mass solution): 133.3 parts

. Propylene Glycol Monomethyl Ether Acetate (PGMEA): 284.9 parts

Further, the dispersion device was operated under the following conditions.

. Bead diameter: φ0.05mm

. Bead filling rate: 75% by volume

. Weekly speed: 10m/sec

. Pump supply: 10kg/hour

. Cooling water: tap water

. Bead mill annular passage internal volume: 0.15L

. The amount of the mixed solution for dispersion treatment: 0.44 kg

After the start of dispersion, the measurement of the average particle diameter was carried out at intervals of 30 minutes (time passed once).

The average particle diameter decreases with the dispersion time (the number of passes), but the amount of change gradually decreases. The dispersion of the primary particle diameter change at the time of extending the dispersion time by 30 minutes was changed to 5 nm or less, and the dispersion was completed. Furthermore, the titanium dioxide particles in the dispersion The primary particle size is 40 nm.

Further, the primary particle diameter of the titanium oxide in the present embodiment means a value obtained by diluting the mixed solution or dispersion containing titanium oxide to 80 times by using propylene glycol monomethyl ether acetate, and using dynamic light scattering method. The obtained dilution was subjected to measurement to obtain a value.

The primary particle diameter of the titanium dioxide was set to the number average particle diameter obtained by the measurement using Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd.

[Preparation of hardenable composition 1]

Using the titanium dioxide dispersion liquid (dispersion composition) obtained above, the components are mixed so as to have the following composition, and a curable composition is obtained.

~The composition of the hardening composition~

. The titanium dioxide dispersion (dispersion composition) prepared above is 81.98 parts

. The following JER-157S65 (Mitsubishi Chemical (share) manufacturing)...3.72

(Polymerizable compound, T-4 in the following table)

. Adhesive polymer...0.44 parts

(M-1 below; weight average molecular weight (Mw) and copolymerization ratio (weight ratio) are as follows)

. Surfactant Megafac F-781 (made by Di Aisheng Co., Ltd.)...0.03

. P-methoxyphenol...0.01 parts

. Propylene glycol monomethyl ether acetate...13.82 parts

Adhesive polymer M-1

(Production of cured film (transparent film))

The curable composition obtained above was applied onto a 12-inch wafer by a spin coating method, and then heated on a hot plate at 100 ° C for 2 minutes to obtain a coating film having a film thickness of 1.05 μm. Further, the coating film was heated at 200 ° C for 5 minutes on a hot plate to obtain a cured film (film thickness: 1.0 μm) as a transparent film.

[Determination of refractive index of transparent film]

With respect to the substrate obtained above, the refractive index of the transparent film for light having a wavelength of 635 nm was measured using an ellipsometer manufactured by J.A. Woollam Japan Co., Ltd.

The results are shown in Table 4 below.

[Evaluation of coated surface shape]

The transparency of the coating film obtained by coating the curable composition as described above was evaluated by visual observation and 5 to 1.

5: No change in transparency, no problem at all levels

4: The transparency of the peripheral part changes slightly, but the central part has no change, and the level of practical use is no problem.

3: A slight change in the peripheral and central parts, but practically no problem.

2: Uneven parts are seen in the peripheral part and the central part, and the practical level is also a problem.

1: There is an uneven part on the entire surface, which is obviously an external level.

The results are shown in Table 4 below.

[Evaluation of solvent resistance of cured film]

The cured film formed in the above manner was immersed in PGMEA for 5 minutes, and the refractive index of the immersed transparent film (cured film) was measured in accordance with the above method. The value of the change in refractive index after the treatment calculated from [the refractive index after solvent immersion] - [the refractive index before solvent immersion] was used as an index of solvent resistance.

The results are shown in Table 4 below.

<Example 2 to Example 82, Comparative Example 1 to Comparative Example 5>

The content of the titanium dioxide of the total solid content of the curable composition, the dispersant (polymer compound (B)), and the type of the polymerizable compound were changed as in the following Table 4, except that Example 2 was prepared according to Example 1. ~Example 82, Comparative Example 1 ~ The curable composition of Comparative Example 5.

In other words, regarding the C-4-modified dispersant (polymer compound (B)) used in Example 1, the use of the titanium dioxide dispersion used in Example 1 was as shown in Table 4 The dispersant (polymer compound (B)) replaces the titanium dioxide dispersion obtained by C-4.

In addition, in Comparative Example 1 and Comparative Example 2, as a dispersing agent different from the polymer compound (B) of the present invention, Solsperse 5000 manufactured by Lubrizol Corporation and DISPERBYK 180 manufactured by BYK Chemical Co., Ltd. were used.

In addition, in the example of the change of the polymerizable compound of the T-4 used in the first embodiment (Example 81, Example 82), in the preparation of the curable composition in Example 1, the following polymerizable compound was used. (T-2, T-3) instead of T-4.

. T-2: The following JER-1031S (manufactured by Mitsubishi Chemical Corporation)

. T-3: EHPE-3150 (manufactured by Daicel Chemical Industry Co., Ltd.; 1,2-epoxy-4-(2-epoxy) of 2,2-bis(hydroxymethyl)-1-butanol Ethyl)cyclohexane adduct)

The content (concentration) of titanium dioxide relative to the total solid content of the curable composition is changed by performing the total amount of titanium dioxide and the dispersant with respect to the total solid content of the curable composition. The total amount in the [preparation of the titanium dioxide dispersion (dispersion composition) of Example 1 was the same, and the increase or decrease of the content of the titanium oxide was supplemented by the increase or decrease of the content of the dispersant, thereby preparing a titanium oxide dispersion.

Further, a transparent film was produced in the same manner as in Example 1 using the obtained curable composition, and evaluated in the same manner as in Example 1. The results are shown in Table 4.

<Example 83>

[Preparation of curable composition 2]

Using the titanium dioxide dispersion liquid (dispersion composition) obtained above, the components are mixed so as to have the following composition to obtain a curable composition.

~The composition of the hardening composition~

. The titanium dioxide dispersion (dispersion composition) prepared above is 81.98 parts

. Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)...3.48

(Polymerizable compound, T-1 in the following table)

. Lanthanide photopolymerization initiator...0.24 parts

(Polymerization initiator, K-1 below)

. Adhesive polymer...0.44 parts

(The above M-1; weight average molecular weight (Mw) and copolymerization ratio (weight ratio) as described above)

. Surfactant Megafac F-781 (made by Di Aisheng Co., Ltd.)...0.03

. P-methoxyphenol...0.01 parts

. Propylene glycol monomethyl ether acetate...12.82 parts

Using the obtained curable composition, a transparent film was separately produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 4.

<Example 84 to Example 88>

The curable composition of Example 84 to Example 88 was prepared in accordance with Example 83 except that the dispersant (polymer compound (B)) and the type of the polymerization initiator were changed as shown in Table 4 below.

In other words, in the preparation of the dispersion agent (polymer compound (B)) of C-4 used in Example 77, in the preparation of the titanium oxide dispersion liquid used in Example 83, the use shown in Table 4 was used. The dispersant (polymer compound (B)) replaces the titanium dioxide dispersion obtained by C-4.

Further, regarding the example of the K-1 change of the polymerizable initiator used in Example 83, in the preparation of the curable composition in Example 83, the polymerization initiator shown in Table 4 was used instead. K-1.

Further, a transparent film was produced in the same manner as in Example 1 using the obtained curable composition, and evaluated in the same manner as in Example 1. The results are shown in Table 4.

As is clear from Table 4, it is understood that Comparative Example 1 and Comparative Example 2 in which the polymer compound (B) is not used have a slightly lower refractive index and a lower coating surface.

In addition, although the dispersing agent satisfies the general formula (1), Comparative Examples 3 to 5 having an acid value of 120 mgKOH/g or more have a high refractive index, but the coating surface shape is slightly unsatisfactory.

On the other hand, it is understood that Examples 1 to 88 using the polymer compound (B) of the present invention have a high refractive index and a particularly good coating surface.

In particular, Examples 1 to 82 using an epoxy compound as a polymerizable compound and Examples 83 to 86 using a fluorene-based compound as a polymerization initiator are excellent in solvent resistance and an epoxy compound is used. The solvent resistance of Examples 1 to 82 which are polymerizable compounds is particularly high.

Further, it was confirmed that a dispersing agent C-5, a dispersing agent C-9, and a dispersing agent having a weight average molecular weight of 5,000 to 8,000 and an acid value of 70 mgKOH/g to 90 mgKOH/g were used. C-20, dispersant C-22, dispersant C-23, dispersant C-31, dispersant C-32, dispersant C-33, dispersant C-42, dispersant C-52, dispersant C- 56. Example 2 of dispersant C-57, dispersant C-60, dispersant C-103, dispersant C-104, dispersant C-107, dispersant C-110~dispersant C-119 6. Example 17, Example 19, Example 20, Example 28, Example 29, Example 30, Example 37, Example 38, Example 41, Example 42, Example 45, Example 50, The curable compositions of Example 60, Example 64, Example 65, Example 68, Example 70 to Example 77, Example 79, Example 81, Example 84, and Example 87, at a wavelength of 400 nm The transmittance of the cured film is 90% or more, and the transmittance of the cured film under visible light is particularly excellent.

In the above embodiments, an example in which a transparent film is formed on a germanium wafer has been described. However, when a solid-state imaging device is fabricated, the germanium wafer is replaced with a photodiode, a light-shielding film, and device protection. The substrate for a solid-state imaging device such as a film may be used.

A light-shielding film containing tungsten which is opened only to the light-receiving portion of the photodiode is formed on the germanium wafer on which the photodiode and the transfer electrode are formed, and covers the entire surface of the light-shielding film formed and the light-receiving portion of the photodiode In the form of (the opening in the light-shielding film), an element protective layer containing tantalum nitride is formed.

Then, the curable composition of the example prepared as described above was applied as a primer layer on the formed element protective layer so that the film thickness became 0.50 μm, and then heated at 100 ° C for 2 minutes using a hot plate. Then, it was hardened by heating at 230 ° C for 10 minutes using a hot plate. By Japanese Patent Special Open 2010-210702 In the method described in the sixteenth aspect, a red color, a blue pixel, and a green pixel having a length of 1.4 μm on one side of the undercoat layer are respectively formed to form a color filter.

The hardenable composition of the example prepared in the above manner was applied onto the color filter so that the film thickness became 1.5 μm, and then heated at 100 ° C for 2 minutes using a hot plate, and then heated at 230 ° C using a hot plate. It hardens for 10 minutes.

Further, coated with HPR-204ESZ-9-5mPa. s (resist liquid manufactured by Fujifilm Electronic Materials Co., Ltd.), and heated at 90 ° C for 1 minute using a hot plate. Using an i-ray stepper (product name: FPA-3000i5+, manufactured by Canon), a mask having a square pattern of 1.4 μm on one side is interposed at 100 mJ/cm ^{2 .} The coated film was exposed. Here, the mask is disposed such that a plurality of square patterns in the mask become positions corresponding to red pixels, blue pixels, and green pixels in the color filter.

The coating film was subjected to a liquid-contact development method at room temperature for 60 seconds using an alkaline developer HPRD-429E (manufactured by Fujifilm Electronic Materials Co., Ltd.), and then sprayed with pure water for 20 seconds by rotary spraying. wash. Thereafter, the substrate is further washed with pure water, and then the substrate is dried by high-speed rotation to form a resist pattern. The post-baking treatment was performed at 200 ° C for 300 seconds using a hot plate to form a resist into a lens shape.

Using a dry etching apparatus (manufactured by Hitachi High-Technologies: U-621), obtained in the above manner under the following conditions The obtained substrate was subjected to a dry etching treatment, and processed in such a manner that a transparent film of the present invention having a high refractive index can be used as a microlens.

. RF power: 800W

. Antenna bias: 100W

. Wafer bias: 500W

. Reaction chamber pressure: 0.5Pa

. Substrate temperature: 50 ° C

. Mixed gas type and flow rate: CF ₄ /C ₄ F ₆ /O ₂ /Ar=175/25/50/200ml/min

. Photoresist etch rate: 140nm/min

If an image is taken using the obtained components, a good image can be obtained.

[Industrial availability]

According to the present invention, it is possible to provide a dispersion composition having a high refractive index and a surface shape of a film surface after coating, a curable composition using the same, a transparent film, a microlens, and a solid-state imaging element.

While the invention has been described in detail with reference to the specific embodiments the embodiments

The present application is based on a Japanese patent application filed on Aug. 31, 2012 (Japanese Patent Application No. 2012-192559), and Japanese Patent Application No. 2013-026068, filed on Feb. Reference is made to this application.

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

16‧‧‧TFT

17‧‧‧ hardened film

18‧‧‧Contact hole

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

Claims (24)

A dispersion composition comprising: a metal oxide particle (A) having a primary particle diameter of 1 nm to 100 nm and being colorless, white or transparent; and an acid value of less than 120 mgKOH/g represented by the following formula (2) Polymer compound (B); and solvent (C), In the above formula (2), R ³ represents a group represented by any one of the following formulae: In the above formula, L ₃ represents a trivalent group; T ₃ represents a single bond or a divalent linking group, and three T ₃ groups may be the same or different; L ₄ represents a tetravalent group; and T ₄ represents For a single bond or a divalent linking group, 4 T ₄ may be the same or different from each other; L ₅ represents a pentavalent group; T ₅ represents a single bond or a divalent linking group, and 5 T ₅ are present It may be the same or different; L ₆ represents a hexavalent group; T ₆ represents a single bond or a divalent linking group, and 6 T ₆ may be the same or different; R ⁴ and R ⁵ are independently represented. a single bond or a divalent linking group; A ² represents at least one selected from the group consisting of an acid group, a ureido group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, and a phenol group. , an alkyl group, an aryl group, a group having an alkoxy chain, an oximine group, an alkoxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, a heterocyclic group, an alkoxydecane group, the group consisting of an epoxy group, an isocyanate group and a hydroxyl group in a monovalent substituent group; n a ² and two R ⁴ may be identical or different; m is a positive number of 8 or less, n is table 1 ~ 9, m + n satisfies 3 ~ 10; P ² represents a polymer chain; m th P ² and R ⁵ may be identical or different. The dispersion composition according to claim 1, wherein the polymer compound (B) has a weight average molecular weight of 5,000 to 8,000. The dispersion composition according to claim 1, wherein the polymer compound (B) has an acid value of 70 mgKOH/g to 90 mgKOH/g. The dispersion composition according to the first aspect of the invention, wherein the content of the metal oxide particles (A) with respect to the total solid content of the dispersion composition is 65 mass% or more. The dispersion composition according to claim 1, wherein A ² in the above formula (2) contains at least one selected from the group consisting of an acid group, a phenol group, an alkyl group, an aryl group, and an alkoxy chain. A monovalent substituent of a group consisting of a group consisting of a hydroxyl group, a hydroxy group, a ureido group, a urethane group, a sulfoximine group, a quinone imine group, and a group having a coordinating oxygen atom. The dispersion composition according to claim 1, wherein A ² in the above formula (2) is a monovalent substituent containing at least one functional group having a pKa of 5 or more. The dispersion composition according to claim 6, wherein the functional group having a pKa of 5 or more is a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, a urea group, an amine group Acid ester group, alkyl group, aryl group, alkoxycarbonyl group, alkylaminocarbonyl group, group having an alkoxy chain, a quinone group, a carboxylate group, a sulfonylamino group, a hydroxyl group or a heterocyclic group . The dispersion composition according to claim 1, wherein the polymer chain represented by P ² is derived from a polymer or copolymer selected from a vinyl monomer, an ester polymer, an ether polymer, A polymer chain of at least one of a urethane polymer, a guanamine polymer, an epoxy polymer, an fluorenone polymer, and the modified or copolymer. The dispersion composition according to claim 1, wherein the polymer chain represented by P ² contains at least one repeating unit, and the repeating number k of the at least one repeating unit is from 3 to 60. The dispersion composition according to claim 1, wherein the polymer compound (B) is a polymer compound represented by the following formula (5): In the above formula (5), R ⁶ represents a group represented by any one of the following formulae: In the above formula, L ₃ represents a trivalent group; T ₃ represents a single bond or a divalent linking group, and three T ₃ groups may be the same or different; L ₄ represents a tetravalent group; and T ₄ represents For a single bond or a divalent linking group, 4 T ₄ may be the same or different from each other; L ₅ represents a pentavalent group; T ₅ represents a single bond or a divalent linking group, and 5 T ₅ are present The same or different; L ₆ represents a hexavalent group; T ₆ represents a single bond or a divalent linking group, and 6 T ₆ groups may be the same or different; R ⁷ to R ⁹ are independently represented. a single bond or a divalent linking group; A ³ represents a monovalent substituent containing at least one acid group; A ⁴ represents a monovalent substituent different from A ³ ; n 1 A ³ and R ⁷ may be the same, N2 A ⁴ and R ⁸ may be the same or different, m is a positive number below 8, n1 is 1~8, n2 is 1~8, m+n1+n2 is 3~10; P ³ The polymer chain is represented; m of P ³ and R ⁹ may be the same or different. The dispersion composition according to claim 1, wherein when the cured film having a film thickness of 1.0 μm is formed by the dispersion composition, the wavelength is from 400 nm to 700 nm with respect to the thickness direction of the cured film. The light transmittance of the region is 90% or more. The dispersion composition according to claim 1, wherein the metal oxide particles (A) are colorless or transparent. The dispersion composition according to claim 1, wherein the metal oxide particles (A) are titanium dioxide particles, zirconium dioxide particles or cerium oxide particles. The dispersion composition according to claim 1, wherein R ³ represents a group represented by any one of the following specific examples (1) to (17): The dispersion composition according to claim 1, wherein the above R ³ represents any one of the following specific examples (1), (2), (10), (11), (16), and (17). The base represented: A curable composition comprising the dispersion composition according to any one of claims 1 to 15, and a polymerizable compound (D). The curable composition according to claim 16, wherein the polymerizable compound (D) is a compound selected from the group consisting of two or more epoxy groups or oxetanyl groups in the molecule, and two or more compounds. At least one of the group consisting of compounds having terminal ethylenically unsaturated bonds. The curable composition according to claim 16, which further comprises at least one selected from the group consisting of a polymerization initiator (E) and a binder polymer. The curable composition according to claim 18, wherein the polymerization initiator (E) is a quinone polymerization initiator. The curable composition according to claim 16, which is used for forming a microlens or an undercoat film for forming a color filter. A transparent film formed using the curable composition as described in claim 16 of the patent application. A microlens formed using a transparent film obtained by the curable composition as described in claim 20 of the patent application. A solid photographic element comprising the microlens of claim 22 of the patent application. A method for producing a dispersion composition, which is a method for producing a dispersion composition according to any one of claims 1 to 15.